NL8502481A - 2,2,6,6-TETRAMETHYLPIPERIDYLAMIDS OF SUBSTITUTED CARBONIC ACIDS AND LIGHT-STABLE, SO STABILIZED POLYMERIC COMPOSITIONS. - Google Patents

Description

* -1- 24948 / Vk / mvl

Short designation: 2,2,6,5-Tetramethylpiperidylamides of substituted carboxylic acids and light-stable, thus stabilized polymeric compositions.

The invention relates to derivatives of 2,2,6,6-tetra-methylpiperidine. More particularly, the invention relates to novel 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids and photostable polymeric compositions thus stabilized.

These compounds can be used as light stabilizers for high molecular weight compounds used in the preparation of polymeric substances such as in the preparation of polymeric films for greenhouses, chemical fibers, articles obtained by injection molding (consisting of various parts, units, tubes ).

Most of the polymeric materials have a low stability to the influence of UV light. As a result, they are quickly attacked causing them to lose properties during use.

In order to obtain photostable compositions based on polymeric materials, special additives such as light stabilizers are added thereto. These additives must have a high light-stabilizing effect.

Currently, o-hydroxybenzophenone (U.S. Patent 3,641,213) and o-hydroxybenzotriazole derivatives (U.S. Patent 3,824,198 and German Patent 2,455,155) are used as light stabilizers for polymeric materials. However, these stabilizers have a low effect.

In recent years, sterically hindered amino derivatives, especially derivatives of 2,2,6,6-tetramethylpiperidine such as esters of 2,2,6,6-tetramethyl 4-hydroxypiperidine and carboxylic acids (see German patents 1,929,928 and 2,258,752 widely used as light stabilizers for polymeric materials such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide and the like. In practice, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, in particular, has been used, known under the trade name "Tinuvin 770" (Modern Plastics, 1975, No. 5, 32). The photostabilizing activity of these compounds is considerably higher than that of o-hydroxybenzophenone and o-hydroxy-SSΰ2 48 1 + "i -2- 24948 / Vk / mvl benzotriazole derivatives. However, these compounds do not provide a sufficiently long operating time to the polymeric materials under conditions of intensive solar irradiation.

The present invention is aimed at obtaining new light stabilizers for polymeric materials that have a high light stabilizing effect.

The compounds of the present invention are new and hitherto unknown from the literature.

The new compounds of the present invention, namely 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids, correspond to the formula 1 stated on the formula sheet, where n = 1 or 2 and where n = 1, A means of one of the radicals, represented on the formula sheet with formulas 2-11 and at n = 2, A has the meaning of a radical of formula 12 or 13 and m = 1 or 2.

The compounds of the present invention are white crystals with a melting point in the range of 82 to 230 ° C, soluble in aliphatic alcohols and chlorinated hydrocarbons.

The structure was confirmed by IR spectroscopy, elemental analysis and molecular weight measurement data.

A photostable polymeric composition containing a polymer and a light stabilizing agent as a stabilizer according to the invention 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids of the above formula in the following amount of the components in parts by weight : 99.0-99.95 parts by weight of polymer and 1.0-0.05 parts by weight of 2,2,6,6-tetramethylpiperidylamide of a substituted carboxylic acid.

Well-known polymers, in particular polyolefins (high and low density polyethylene, polypropylene and copolymers thereof), polystyrene and copolymers thereof, polyvinyl chloride, polyamides, polyurethanes and the like can be used as a polymer.

In order to improve the thermal stability of the photostable polymeric composition according to the invention, it is recommended that the thermo-stabilizing agents are also incorporated herein in an amount of 0.05 to 0.3% by weight, based on the polymer. . As thermo-stabilizing compounds, compounds can be used selected from the well-known group of thermo-stabilizing agents such as sterically hindered phenol derivatives such as tetraester of 3,5-di-tert-butyl 4-hydroxyphenylpropionic acid and pentaerythritol (Irganox 1010), as 82 4 8 1 '# * -3- 24948 / Vk / mvl octadecyl ester of 3,5-di-tert-butyl 4-hydroxyphenylpropionic acid (Irganox 1076), 2,2'-methylene bis- (4-methyl 6-tert. butylphenol) (A0-2246), phosphites such as tri- (paranonylphenyl) phosphite (Polygard) and the like.

In order to improve the light stabilizing effect, it is recommended to also add UV light absorbing agents (UV absorbers) to the light stable polymeric compositions in an amount of 0.1 to 0.3 wt. .% of the polymer. As UV absorbers, o-hydroxybenzophenone derivatives such as 2-hydroxy 4-octyloxybenzophenone (Cyasorb UV 531) and o-hydroxybenzo-10 triazole derivatives such as 2- (3 ', 5'-ditert-butyl 2'-hydroxyphenyl) can be used. 5-chlorobenzotriazole (Tinuvin 327) or 2- (2'-hydroxy 5'-methylphenyl) benzotriazole (Tinuvin P).

The amount of light stabilizing agent, especially 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids as well as heat stabilizing and UV absorbing agents, is limited by obtaining maximum stabilizing action and, on the other hand, by economic considerations for efficient use of the composition.

The polymeric materials stabilized with the compounds of the invention can be used as a variety of objects such as films, fibers, plates, bars.

The photostable polymeric compositions stabilized with 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids of the present invention are 1.5-4 times better in light stability than photostable polymeric compositions which are stabilized with o-hydroxybenzophenone and o-hydroxybenzotriazole derivatives and 10-15% better than the composition based on esters of 2,2,6,6-tetramethyl 4-hydroxypiperidine and carboxylic acids. Furthermore, 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids of the present invention have a thermostabilizing effect on polystyrene containing plastics.

The method of preparing 2,2,6,6-tetramethylpiperidylamides of substituted carboxylic acids as well as the method of preparing photostabilized polymeric compositions are simple using standard equipment and these methods can be carried out as follows.

The method of preparing the compounds of the present invention is based on a known reaction in which the S? A O A a 1

* - -V

--4- 24948 / Vk / mvl amidation of acids or the low esters is performed by running 2,2,6,6-tetra-methyl 4-aminopiperidine (triacetone diamine) at a temperature between 170 and 210 ° C, simultaneously by distilling off the released lower alcohol or water (Veigand- "Hilgetag Experimental Methods 5 in Organic Chemistry", "Khimiya" Publishers, Moscow, 1968, biz. 445, 454.

The desired products are separated by recrystallization from an organic solvent.

The light stabilized polymeric compositions are prepared according to standard industrial processes. The light stabilizer 10 is supplied to the polymer during the preparation of the polymer or when processing it into an article. The process is performed using standard equipment (extruder, mill, injection molding machine). The stabilizing agent can be added to the polymer individually or in the form of a solution or suspension in a corresponding solvent or dispersant.

Thermo-stabilizers and UV absorbers can both be supplied during polymer preparation and polymer processing.

The invention is further illustrated by the following examples.

Example I

A 100 ml three-necked flask equipped with a stirrer, thermometer Würtz packing with reflux condenser and a collecting vessel was charged with 15.62 g of triacetone diamine and 18.39 g of ethyl ester of N-cyclohexylaminoacetic acid-25 and heated at a temperature of 180 to 210 ° C to no more ethanol was released. After cooling the reaction mixture, the product was recrystallized from toluene to obtain 25.1 g (85% of the theoretical amount, based on triacetone diamine) of the desired product, namely 2,2,6,6-tetramethylpiperidylamide of N- cyclohexyl-30 aminoacetic acid (compound 1) with a melting point of 83 ° C.

The elemental analysis data for the compound of formula C ^ H ^ N ^ O were: C (%) H (%) N (%) calculated: 69.11 11.26 14.23 35 found: 68.98 11.56 14.08.

The molecular weight found was 290.7, while the calculated molecular weight was 295.47.

85 02 48 1 '* - * s -5- 24948 / Vk / mvl

The data concerning the IR spectrum were: _ (amide 1) = 1665 cm \ 6 (amide 2) = 1510 cm \ ^ = u ^ Wn v, JCJ = 3360 cm ”.

Example II

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of N-morpholine acetic acid (Compound 2), was obtained by following the procedure described in Example I, from 15.62 g of triacetone diamine and 17, 28 g of N-morpholinoacetic acid ethylate. The desired product was obtained in an amount of 26.24 g (92.6% of the theoretical amount based on triacetone diamine) with a melting point after recrystallization from toluene of 103 ° C.

The elemental analysis data for the compound of formula C ^ 5 ^ 39 ^ 3¾ were: C (%) H (%) N (%) 15 calculated: 63.57 10.31 14.82 found: 63.74 10.28 14.48.

The molecular weight found was 317.8 while the calculated molecular weight was 283.42.

The data from the IR spectrum were: 20 \> "_ (amide 1) = 1685 cm δλ." (Amide 2) = s 1515 cm \ L = U u Nri VNH S 3385 Cm "*

Example III

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of N-piperidinoacetic acid (compound 3), was prepared in the same manner as in Example 1 from 62.5 g of triacetone diamine and 68.34 g of N -piperidinoacetic acid ethylate. The yield of the desired product was 90.74 g (80.6% of the theoretical amount, based on triacetone diamine). The melting point was 77 ° C (toluene).

The data from the elemental analysis for the compound of formula C ^ H ^ N ^ O were: C (%) H (%) N (%) calculated: 68.28 11.10 14.93 found: 68.61 10.91 14.83.

The molecular weight found was 280.4 while the calculated molecular weight was 281.45.

85 (52 4 3 * -6- 24948 / Vk / mvl

The data from the IR spectrum were: -1 -1 0 (amide 1) = 1680 cm, 6.t "(amide 2) = 1510 cm, L = U 1 Nn VNH = 3375 C" "

Example IV

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of aniline acetic acid (Compound 4), was prepared by following the procedure described in Example I starting from 23.44 g of triacetone diamine and 26 .8 g of anilinoacetic acid ethylate.

The yield of the desired product was 35.7 g (82.2% of the theoretical amount, based on triacetone diamine). The melting point was 175 ° C (isopropanol).

The elemental analysis data for the compound of formula C ^ H ^ N ^ O were: C (%) H (%) N (%) 15 calculated: 70.55 9.40 14.52 found: 70.34 9.96 14.68.

The molecular weight found was 282.5, while the calculated molecular weight was 289.4.

The data from the IR spectrum were: -1 -1 20 _ (amide I) = 1655 cm, <5.Ttr (amide 2) = 1500 cm, L-U-JNn v. "= 3390, 3440 cm".

Want

Example V

The compound of this example, namely N, N'-bis- (2,2,6,6-tetramethylpiperidyl) -acetamide of piperazine (compound 5) was prepared following the procedure described in Example I by starting from 31.25 g of triacetone diamine and 25.75 g of N, N'-piperazinodiacetic acid diethylate.

The yield of the desired product was 37 g (77.3% of the theoretical amount, based on triacetone diamine) with a melting point of 230 ° C (toluene).

The data from the elemental analysis for the compound of formula ^ 26 ^ 50 ^ 6 ^ 2 were: C (%) H (%) N (%) calculated: 65.23 10.53 17.55, found: 65, 30 10.60 17.78.

The molecular weight found was 472.5, while the calculated molecular weight was 478.7.

85 0 2 4 8 f

V

-7- 24948 / Vk / mvl

The data from the IR spectrum were: v_ (amide 1) = 1650 cm-1, <5.m (amide 2) = 1530 cm -1, 1500 cm 1.

U = U ^ Nn VHH = 3350

Example VI

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylaraide of N-cyclohexylaminopropionic acid (compound 6), was prepared in the manner described in Example I starting from 31.25 g of triacetone diamine and 37 0.05 g of N-cyclohexylaminopropionic acid methylate. The yield of the desired product was 53.4 g (86.4% of the theoretical amount based on triacetone diamine) with a melting point of 122 ° C.

The elemental analysis data for the compound of formula were: C (%) H (%) N (%) calculated: 69.85 11.40 13.58 found: 69.55 11.32 13.43.

The molecular weight found was 308.2 while the calculated molecular weight was 309.5.

The data from the IR spectrum were: vc_0 (amide 1) = 1670 cm -1, δ ^ (amide 2) = 1560 cm -1, 20 vNH = 3240, 3320 cm -1.

. Example VII

The compound of this example, N, N'-bis- (2,2,6,6-tetramethylpiperidyl) propionamide of piperazine (compound 7), was prepared in a manner similar to that described in Example I from 31.25 g of triacetone diamine and 25.8 g of N, N * -piperazinodipropionic acid dimethylate.

The yield of the desired product was 34.4 g (68% of the theoretical amount, based on triacetone diamine) with a melting point of 161 ° C (toluene).

The elemental analysis data for the compound of formula C-qR-.N.-O- were: 28 54 6 2 C (%) H (%) N (%) calculated: 66.36 10.74 16 58 found: 66.64 10.71 16.01.

The molecular weight found was 502.3, while the calculated molecular weight was 506.78.

853243! -8- 24948 / Vk / mvl

The data from the IR spectrum were: -1 -1 (amide 1) = 1650 cm, (amide 2) = 1530 cm, vra = 3300, 3400 cm-1.

NH

Example VIII

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of benzylaminopropionic acid (compound 8), was prepared following the procedure described in Example I starting from 46.9 g of triacetone diamine and 58 g benzylaminopropionic acid methylate. The yield of the desired product was 73.14 g (76.8% of the theoretical amount based on triacetone diamine) with a melting point of 132 ° C (toluene).

The elemental analysis data for the compound of formula C ^ H ^ N ^ O were: C (%) H (%) N (%) 15 calculated: 71.88 9.84 13.24 found: 71.92 9.68 13.71.

The molecular weight found was 318.5 and the calculated molecular weight was 317.5.

The data from the IR spectrum were: -1 -1 20 (amide 1) = 1660 cm, <5.m (amide 2) = 1565 cm, LU - Nti v ... T = 3330 cm ".

NH

Example IX

The compound of this example, namely 2,2,6,6-tetramethylpiperidylamide of N-morpholinopropionic acid (compound 9), was prepared following the procedure of Example I starting from 15.62 g of triacetone diamine and 17.32 g of N-morpholinopropionic acid methylate. The desired product was obtained in an amount of 27 g (90.8% of the theoretical amount, based on triacetone diamine) with a melting point of 82 ° C (isopropanol).

30 The data from the elemental analysis for the compound of formula Ο., Η-, Ν, Ο- were: 16 31 3 2 C (%) H (%) N (%) calculated: 64.61 10.51 14 , 13 found: 64.45 10.26 14.22.

The molecular weight found was 298.5 and the calculated molecular weight was 297.4.

8532 4 3 1 -9- 24948 / Vk / mvl

The data from the IR spectrum were: v '(amide 1) = 1630 cm 1, 5' (amide 2) = 1510 cm 1,

UU WH

V, tu = 3450, 3270 cm.

NH

Example X.

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of N-piperidinopropionic acid (Compound 10), was prepared in the manner indicated in Example I starting from 31.25 g of triacetone diamine and 34 20 g of N-piperidinopropionic acid methylate. The yield of the desired product was 29.3 g (49.6% of the theoretical amount, based on triacetone diamine) with a melting point of 133 ° C (hexane).

The elemental analysis data for the compound of formula were: C (%) H (%) N (%) Calculated: 69.11 11.26 14.22 Found: 69.47 11.84 14.63-

The molecular weight found was 298.3 and the calculated molecular weight was 295.47-

The data from the IR spectrum were: υ_ _ (amide 1) = 1630 cm-1, <5.T (amide 2) = 1520 cm @ 20 vNH = 3400, 3250 cm.

Example XI

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of 2 ', 2', 6 ', 6'-tetramethylpiperidylaminopropionic acid (compound 11), was prepared in the manner described in Example I by of 31.25 g of triacetone diamine and 8.6 g of methyl acrylate.

The desired product was obtained in an amount of 29.33 g (80% of the theoretical amount, based on methyl acrylate), mp 139 ° C (ethyl acetate).

The data from the elemental analysis for the compound of formula 1 ^ 42 ^ 0 were: C (%) H (%) N (%) calculated: 68.80 11.55 15.28 found: 68.75 11. 62 15.47.

The molecular weight found was 365.8 and the calculated molecular weight was 366.6.

The data from the IR spectrum were: (amide 1) = 1660 cm \ (amide 2) = 1510 cm * "1, v = 3260, 3" 5 cm "1.

8502 48 1 9 -10- 24948 / Vk / mvl

Example XII

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of phenoxyacetic acid (Compound 12), was prepared according to the procedure described in Example I starting from 15.21 g of phenoxyacetic acid and 15> 82 g triacetone diaraine. The yield of the desired product was 24.5 (84.3% of the theoretical amount, based on tri-acetone diamine) with a melting point of 85 ° C (toluene).

The elemental analysis data for the compound of formula C ^ H ^ N ^ were: 10 C (%) H (%) N (%) calculated: 70.31 9.02 9.65 found: 69.91 8 , 91 9.48.

The molecular weight found was 307.0 and the calculated molecular weight was 290.41.

The IR spectrum data were: -1 -1 vc_0 (amide 1) = 1670 cm, (amide 2) = 1500 cm, v = 3290 cm-1.

Example XIII

The compound of this example, namely 2,2,6,6-tetramethyl-piperidylamide of phenylthioacetic acid (compound 13) was prepared in the manner as described in Example I starting from 15.62 g of triacetone diamine and 20.6 g phenylthioacetic acid ethylate. The yield of the desired product was 23.25 g (75.9% of the theoretical amount, based on triacetone diamine), mp 94 ° C (hexane).

The data from the elemental analysis for the compound of formula were: C (%) H (%) N (%) S (%) calculated: 66.62 8.55 9.14 10.46 found: 66.35 8.61 9.08 10.23.

The molecular weight found was 303.4 and the calculated molecular weight was 306.47.

The data from the XR spectrum were: -1 -1 V- _ (amide 1) = 1680 cm, δ.τ “(amide 2) = 1505 cm,

C = 0. NH

VM "= 3420, 3220 cm".

NH

Example XIV

The compound of this example, namely 2,2,6,6-tetraraethyl-piperidylamide of n-tert-butylphenoxyacetic acid (compound 14), was prepared in the manner described in Example I starting from 15.62 g of 8502461 - 11-244948 / Vk / mvl triacetone diamine and 23.7 g n-tert-butylphenoxyacetic acid ethylate. The yield of the desired product was 19.9 g (57.4% of the theoretical amount, based on triacetone diamine) with a melting point of 88 ° C (hexane).

The data from the elemental analysis for the compound of formula N_0n were: 21 34 2 2 C (%) H (%) N (%) calculated: 72.79 9.89 8.08 found: 72.70 9. 94 8.08.

The molecular weight found was 349.10 and the calculated molecular weight was 346.52.

The IR spectrum data were: vc_0 (amide 1) = 1685 cm -1, (amide 2) = 1530 cm -1, v 5 3430 cm-1.

15

Example XV

The compound of this example, namely bis- (2,2,6,6-tetra-methylpiperidylacetamido) -2 ', 2'-phenoxypropane (compound 15) was prepared following the procedure set forth in Example I by 15.52 g of triacetone diamine and 18.42 g of 4,4'-diphenyloxypropionic acid diethylate. The yield of the desired product was 27.6 g (89% of the theoretical amount, based on triacetone diamine) with a melting point of 79 ° C (gas oil / toluene).

The elemental analysis data for the compound of formula CL-H ^ fLO were: 25 C <%> H (%) N (%) calculated: 71.58 9.09 9.02 found: 71.44 9 , 8.86.

The molecular weight found was 627.00 and the calculated molecular weight was 620.88.

30

The data from the IR spectrum were: V- (amide 1) = 1670 cm "1, (amide 2) = 1520 cm" 1,

C = 0. NH

υΝΗ = 3430, 3270 cm.

Example XVI

The compound of this example, 2,2,6,6-tetramethyl-35-piperidylamide of β- (2 *, 2 ', 6'-tetramethylpiperidylamino] crotonic acid (compound 16), was prepared in the manner described in Example I by starting with 65.07 g of acetoacetic acid ether and 156.26 g of triacetone-8502481 -12- 24948 / Vk / mvl diamine The yield of desired product was 115.3 g (61.0% of the theoretical amount calculated on triacetone diamine) with a melting point of 202 ° C (isopropanol).

The elemental analysis data for the compound of the formula: ^ 22 ^ 42 ^ 4 ^ were: C (%) H (%) N (%) calculated: 69.79 11.18 14.80 found: 69.94 11.20 14.70.

The molecular weight found was 388.0 and the calculated molecular weight was 378.61.

The data from the IR spectrum were: -1 -1 V- Λ (amide 1) = 1680 cm, (amide 2) s 1520 cm, w — U 4 Nil j VNH = Cm * VC-C = Cm *

Example XVII 15

Of compound 11, 0.3 g of 2,2,6,6-tetra-methylpiperidylamide of 21.2 · 6 *, 6'-tetramethylpiperidylaminopropionic acid was dissolved in acetone and added to 99.7 g of powdered polypropylene.

The resulting mixture was stirred under evaporation of acetone and then added to a laboratory mixer and mixed therein for 30 minutes. Thus, a homogeneous mass was obtained from which films were made with a thickness of 120 µm by injection molding under compression at a temperature of 210 + 2 ° C. The films were then subjected to an aging by photo-oxidation in a test according to Xenotest 1200 to determine weather resistance. The degree of attack of the films was determined using an IR spectrometer by determining the time after which the carbonyl index was equal to 0.3.

Following the above-mentioned method, light stable polymeric films were obtained with other light stabilizers of the invention (compounds 12, 14, 15).

To determine the light stabilizing action of the agents of the invention, photostable films were prepared using the conventional stabilizers Tinuvin 327, Tinuvin 770 and

Cyasorb UV-531 in a similar manner.

35

The results obtained from these experiments are summarized in Table A.

8502 48 1 _13_ 24948 / Vk / mvl

TABLE A

. time for the preparation experiment to stabilize amount of stabilizer of the care-ionizing agent liser (parts by weight) index of 0.3 (hours) 5 1 Tinuvin 327 0.3 130 2 Cyasorb OV-531 0.3 210 3 Tinuvin 770 0.05 240 10 4 Tinuvin 770 0.1 380 5 Tinuvin 770 0.3 500 6 Tinuvin 770 1.0 650 7 compound 11 0.05 275 15 8 compound 11 0.1 420 9 compound 11 0.3 530 10 connection 11 1.0 720 11 connection 12 0.1 460 20 12 connection 12 0.3 625 13 connection 12 1.0 750 14 connection 14 0.1 420 25 15 connection 14 0.3 545 16 compound 14 1.0 760 17 compound 15 0.05 310 18 compound 15 0.3 540 30 19 compound 15 1.0 780

The data in Table A shows that the light stabilizing effect of polypropylene films stabilized with compounds 11, 12, 14 and 15 is approximately 2.5 times better than the light stability of 35 films stabilized with Cyasorb UV-531 and about 15% better than the light stability of films stabilized with Tinuvin 770.

- · *. * ..

^ 1 -14- 24948 / Vk / mvl 9

Example XVIII

0.1 g of compound 12, namely 2,2,6,6-tetramethylpiperidylamide of phenoxyacetic acid, was dissolved in ethanol and added to 99.9 g of high density polyethylene in powder form. Ethanol was removed from the resulting mixture under reduced pressure. Thus, a homogeneous mass was obtained from which films were made with a thickness of 100 µm, which were formed under pressure at a temperature of 160 ° C, while the pressure was 150 kg / cm. The films were subjected to an aging according to a Xenotest 150 by light oxidation to determine the weather resistance. The extent of attack of the films was determined using an IR spectrometer by determining the time within which the carbonyl index of 0.3 was reached and by the time course until decomposition took place.

Following this method, photostable polymeric films were also prepared using other light stabilizers of the invention (compounds 2, 3, 7> 9> 13 and 16) and, for comparison, the actions of anti-stabilizers were determined. light, namely Tinuvin 770 and Cyasorb UV-531.

The results obtained are shown in Table B.

S 5 0 2 4 8 1 -15- 24948 / Vk / mvl

TABLE B

I,. ,,, time for it ......

| to reach the film against light quantity of stabilizing stabilizer ",,. . of the structural means (parts by weight) (s) | 1 Cyasorb UV-531 0.1 975 1700 2 Cyasorb UV-531 0.3 1250 2500 T0 3 Tinuvin 770 0.05 1100 1900 4 Tinuvin 770 0.15 1550 2895 5 Tinuvin 770 0.3 1850 3350 6 Tinuvin 770 1, 0 2100 3900 15 7 connection 16 0.15 1750 3250 8 connection 16 0.3 2050 3700 9 connection 12 0.3 1795 3360 10 connection 12 1.0 2420 4500 ^ 11 connection 2 0.05 1230 2100 12 connection 2 0, 3 1995 3685 13 connection 2 0.5 2070 3885 14 connection 3 0.05 1250 2155 25 15 connection 3 0.1 1695 2475 16 connection 3 1.0 2360 4295 17 connection 7 0.1 1710 3200 2Q 18 connection 7 0, 3 2100 3685 19 connection 9 0.1 1720 3340 20 connection 9 0.5 2000 3580 21 connection 13 0.3 1920 3380 35 22 connection 13 1.0 2000 3955 ----- 8502 48 1 -16- 24948 / Vk / mvl

The data in Table B shows that the stability of the films to light in low density polyethylene stabilized with compounds 2, 3, 7, 9, 12 and 16 is about 1.5 times better than in films stabilized with Cyasorb UV-531 and about 10% better than the stability of the films stabilized with Tinuvin 770.

Example XIX

From compound 6, namely 2,2,6,6-tetramethylpiperidylamide of N-cyclohexylaminopropionic acid, 0.05 g was dissolved in acetone and added 10 to 99.75 g of powdered polypropylene together with 0.2 g of phenol stabilizing agent Irganox 1010 The resulting mixture was mixed to evaporate acetone and then added to a laboratory mixer and mixed therein for 30 minutes. Thus, a homogeneous mass was passed through an extruder at a temperature (in the zones) of 210 to 220 ° C to obtain granules. These granules or granules were fed to a melt section of a laboratory scale fiber-forming apparatus. The single fiber that was extruded from the die was cooled in a water bath at a temperature of 18-20 ° C and then subjected to a quadruple stretch at a temperature of 130 ° C. The obtained single fibers with a linear density of 8 tex were subjected to a destruction or attack by photo-oxidation according to a Xenotest 1200 to determine the weathering resistance. The degree of attack of the single fibers was determined by determining the toughness retention value after 400 hours of irradiation (expressed in percent).

Following the above method, single fibers were prepared using light stabilizers of the present invention (compounds 1, 4, 5, 6, 10, 13, 15) and using other thermo-stabilizers such as Irganox 1076.

To determine the stabilizing effect against light, fibers were stabilized with Irganox 1010 and with Tinuvin 327 and Tinuvin 770 in a similar manner.

The results obtained are shown in Table C.

83 0 2 48 1 -17- 24948 / Vk / mvl

TABLE C

quantity of stability (%) after 400 theorem components of the sator (parts by weight) irradiation for hours 5 1 Tinuvin 327 0.3 pn 0

Irganox 1010 0.2 "

2 Tinuvin 770 0.1 Q2 Q

Irganox 1010 0.3 '

3 Tinuvin 770 0.2 6o Q

IQ Irganox 1010 0.1 "

4 Tinuvin 770 1 * 0 Q

Irganox 1010 0.05 "

Compound 15 0.05 - Q

Irganox 1010 0.3 '

15 6 compound 15 0.2 75 Q

Irganox 1010 0.1 "

7 compound 15 0.5 Qo Q

Irganox 1010 0.2 "

8 compound 15 1.0 03 Q

20 Irganox 1010 0.05 '9 compound 4 0.1 - -

Irganox 1010 0.05 "

10 compound 5 0.2 Q

Irganox 1010 0.1 '25 11 compound 13 0.3 - -

Irganox 1076 0.3 *

12 compound 10 1.0 80 Q

Irganox 1076 0.05 '13 compound 6 0.05 72 0 30 Irganox 1076 0.2' 14 compound 1 0.2 7n n

Irganox 1076 0.1 "

The data in Table C shows that the light stability of the fibers stabilized with compounds 1, 4, 5, 6, 10 and 15 of the invention is 3 to 4 times better than with fibers stabilized with Tinuvin 327 and about 15% better than fiber stabilized with Tinuvin 770.

: 2 48 1 t.

-18- 24948 / Vk / mvl

Example XX

Compound 14, namely 2,2,6,6-tetramethylpiperidylamide of n-tert-butylphenoxyacetic acid, was added in an amount of 0.2 g to 99.95 g of high density polyethylene in a roll mill after 3 minutes 5 times together with 0.2 g of Cyasorb CJV-531 and 0.05 g of A0 2246. The polymeric composition was prepared at a roll temperature of 160 ° C with continuous tissue cutting for 10 minutes. From the milled tissue of the polymer, 2 mm plates were formed under compression at a temperature of 160 ± 2 ° C and samples were cut from both sides. The samples were subjected to an aging by photo-oxidation according to the Xenotest 1200 in a room to determine the weather resistance for 2000 hours.

The degree of attack of the samples was determined by determining the relative elongation that was retained at break after 200 hours of aging.

The photostable compositions with other light stabilizers of the invention and known additives such as Tinuvin 327, Cyasorb UV-531 and Tinuvin 770 were prepared in a similar manner.

20 The results obtained are summarized in Table D.

.2 48 1 -19- 24948 / Vk / mvl TABLE D __ j - “-” “[maintain relative amount of stabilization (%) at break component liser (parts by weight) after aging during theorem 2000 hours 3 1 Gyasorb UV-531 0.1 5.7 AO-2246 ° '05 2 Cyasorb UV-531 0 * 2 7.0 10 AO-2246 ° '05 3 Cyasorb UV-531 0.3 8.0 AO- 2246 ° * 05 15 "- 4 Tinuvin 327 0> J broken after 2000 hours AO-2246 ° '05 on 5 Tinuvin 770 0.1 10.0 AO-2246 0.05 5 Tinuvin 770 °> 2 21.5 25 AO -2246 0.05 7 Tinuvin 770 °, 3 44.8 AO-2246 ° * 05 30 3 compound 11 0 »1 14.8 AO-2246 0.05 35 g compound 11 0.2 27.0 AO-2246 0 .05 in 10 compound 11 0.3 55.6 U AO-2246 0.05 11 compound IA 0.1 10.5 45 AO-2246 0.05 12 compound 14 0.2 23.6 AO-2246 0.05 50 13 compound 14 0.3 45.0 AO-2246 0.5 55 i4 Tinuvin 770 0.2

Tinuvin 327 0.2 'AO-2246 0.05 60 15 Tinuvin 770 0.1

Cyasorb UV-531 0.1 58, AO-2246 0.05 55 -55 Tinuvin 770 0.2

Cyasorb UV-531 0.2 78.0 AO-2246 0.05 17 Tinuvin 770 0.3

Cyasorb UV-531 0.3 80.0 AO-2246 0.05 f5 13 Tinuvin 770 0.3

Cyasorb UV-531 0.1 70.0 AQ-2246 0.05 80 19 Tinuvin 770 0.1

Cyasorb UV-531 0.3 67.5 AO-2246 0.05 S3 0 2 4 8 1 9 -20- 24948 / Vk / mvl \ TABLE D (continued) Retain Relative Amount of Stabilization (%) at Break theorem components and sator (parts by weight) after aging for 5 2000 hours 20 Tinuvin 770 0.1 10 Tinuvin 327 0.3 62.0 AO-2246 0.05 21 compound 11 0.1 15 Cyasorb UV-531 0.1 67.9 AO-2246 0.05 22 compound 11 0.2 20 Cyasorb UV-531 0.2 88.2 AO-2246 0.05 23 compound 11 0.2 25 Tinuvin 327 0.2 82.0 AO- 2246 0.05 24 compound 11 0.3 30 Cyasorb UV-531 0.3 90.0 AO-2246 0.05 25 compound 11 0.3 35 Cyasorb UV-531 0.1 71.9 AO-2246 0.05 26 compound 11 0.1 40 Cyasorb UV-531 0.3 72.5 AO-2246 0.05 27 compound 14 0.1 45 Tinuvin 327 0.1 56.5 AO-2246 0.05 28 compound 14 0.1 50 Cyasorb UV-531 0.1 60.0 AO-2246 0.05 29 Compound 14 0.2 55 Cyasorb UV-531 0.2 80.5 AO-2246 0.05 60 The data in Table D shows that the stability to light of plates made of low density polyethylene stabilized with the compound 11 and 14 according to the invention, is about 3 times better than the stability to light of plates stabilized with Cyasorb UV-531 or with Tinuvin 327 and about 10% higher in 65 compared to plates obtained using Tinuvin 770 as stabilizer .

85 02 48 1 -21- 24948 / Vk / ravl * 1, r '

Example XXI

Compound 16, namely 2,2,6,6-tetramethylpiperidylamide of 3- (2 ', 2', 6 ', 6'-tetramethylpiperidylamine) crotonic acid, was added in an amount of 1.0 g together with 0.1 g Tinuvin 327 and 0.05 g Irganox 1010 was added to 98.85 g of powdered polypropylene. The resulting mixture was stirred, granulated, and 10 tex single fibers were formed therefrom by following the procedure described in Example XIX.

The single filaments or fibers were subjected to aging by photo-oxidation according to the Xenotest 1200 in a room 10 to determine the weather resistance for 500 hours.

The light stabilizing effect of the additive was determined by the percentage retention of the toughness of the single fibers after breakage.

Following the above-mentioned method, photostable compositions were prepared and tested with other stabilizers according to the invention and with known additives, namely Tinuvin 327, Cyasorb UV-531 and Tinuvin 770.

The results obtained are summarized in Table E.

The data of Table E shows that the single wires stabilized with compounds 8, 9, 11, 15, 16 of the present invention are 2-4 times more stable to light than the wires stabilized with Tinuvin 327 or Cyasorb UV -531 and are about 15% more stable to light than wires stabilized with 25 Tinuvin 770.

5302 48 1 t -22- 24948 / Vk / mvl

TABLE E

, ,,. ,, ... maintain toughness together. amount of stable,. , * components *, after irradiation by spraying sacor; 50Q hours (%) ran 5 ---- 1 Tinuvin 327 0.3

Irganox 1010 0.1 2 Cyasorb UV-531 0.3

Irganox 1010 0.1 10 3 Tinuvin 770 0.05

Tinuvin 327 0.3 70

Irganox 1010 0.05 4 Tinuvin 770 1.0

Tinuvin 327 0.1 76

Irganox 1010 0.05 15 5 Tinuvin 770 0.1

Cyasorb UV-531 0.2 72

Irganox 1010 0.3 6 compound 15 0.05

Tinuvin 327 .0.3 82 2Q Irganox 1010 0.05 7 compound 16 1.0

Tinuvin 327 0.1 90

Irganox 1010 0.05 8 compound 8 0.1

Cyasorb UV-531 0.2 87 25 Irganox 1010 0.3 9 Compound 9 0.05

Cyasorb UV-531 0.3 85

Irganox 1010 0.05, compound 11 0.1

Cyasorb UV-531 0.3 88 30 Irganox 1010 0.1 83 02 48 1 4. -23- 24948 / Vk / mvl

Example XXII

0.1 g of the compound 5, namely N, NT-bis (2,2,6,6-tetramethylpiperidyl) -acetamide piperazine, was added to 99.9 g of granulated impact resistant polystyrene. A 5% solution in benzene was prepared from the resulting mixture. After completely dissolving the impact-resistant polystyrene and the stabilizing additive, films were made with a thickness of 70 µm by pouring the solution.

After evaporating the solvent (about 2 days), the obtained films were subjected to an aging by irradiation under the influence of light under unfiltered UV light. The degree of attack of the films was determined on an IR spectrometer by determining the carbonyl groups at 1720 cm -1 (relative units) and by retaining the double bonds (C = C bonds) at 900 cm -1 ( as a percentage of the initial value) after 100 hours of aging.

Photostable compositions were prepared using the above method with other photostabilizers of the present invention and for comparison with a known stabilizer, namely Tinuvin P.

The results obtained are summarized in Table F.

20 TABLE F

~, ~ ~ combination keep double light of carbonyl bonds (% of stabilizer, groups (% of the number in __m (Sew.dl »n) ds beglMaarde) the beginning) 25 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 11 0.05 4.1 45 30 6 compound 11 0.30 3.0 69 7 connection 3 0.10 3.7 59 8 connection 4 0.30 3.1 65 9 connection 5 0.30 2.8 80 10 connection 13 0.10 3.4 62 35 11 connection 8 0.05 4. 8 42 12 connection 10 1.00 1.7 92 13 connection 10 0.30 2.7 82 3502 48 1

a

-24- 24948 / Vk / mvl

The data in Table F shows that Compounds 3, 4, 5, 8, 10 and 11 of the present invention impart a light stability to the impact resistant polystyrene about 2-3 times higher than the value obtained with Tinuvin P.

Example XXIII

Samples of impact resistant polystyrene films were prepared according to the procedure described in Example XXII. Heat resistant compositions were prepared using stabilizers according to the present invention and a known stabilizer, namely Polygard, was used to compare the stabilizing activity.

The films were subjected to thermal aging at a temperature of 120 ° C in an air thermostat. The degree of degradation of the films was determined as described in Example XXII after 500 hours of thermal aging.

The results of the experiments are shown in Table G.

TABLE G

content of combination double bond no. "compound curing agent 1" of gene C = C retained 20 ew? deenophonyl groups 1 Polygard 0.05 broken broken 2 Polygard 0.10 5.0 29 3 Polygard 0.30 5, 2 31 25 4 Polygard 0.50 3.4 37 5 Polygard 1.00 2.9 41 6 Connection 16 0.05 3.2 49 30 7 Connection 5 0.10 2.5 53 8 Connection 14 0.30 1. 9 67 9 connection 15 0.50 1.7 77 10 connection 9 1.00 1.3 81 35 ------

The data in Table G shows that compounds 5, 9, 11, 14 and 15 are 1.5-2 times more effective than the stabilizing action of Polygard.

3302481 -25- 24948 / Vk / mvl

/ example XXIV

0.5 g of compound 12, namely 2,2,6,6-tetramethylpiperidylamide of phenoxyacetic acid, was added to 99.5 g of ternary copolymer (composition 54 parts by weight styrene, 28 parts by weight acrylonitrile, 1-8 parts by weight Polybutadiene). The mixture was mixed in a ball mill and mixed in a mixer at a temperature of 190 to 210 ° C. Standard bars were injection molded (50 x 6 x 4 mm) from the mixture thus prepared. The bars were subjected to light aging using carbon arc lamps for 200 hours.

After aging, the bars were subjected to a drop test to determine the spring force expressed in kgf / cm (in percent of the initial value) using a pendulum hammer.

The same procedure was followed for the preparation and examination of photostable compositions with other photo-stabilizers according to the invention and with a known photo-stabilizer, Tinuvin P.

The results of these experiments are shown in Table H.

TABLE H

20 against light stabilizing stability (%) of lisating agent («« .dJlen) ie ^ "^ rde 1 Tinuvin P 0.05 29 2 Tinuvin P 0.10 34 25 3 Tinuvin P 0.50 47 4 Tinuvin P 1.00 50 5 compound 11 0.05 41 6 compound 1 0.10 68 30 7 compound 13 0.50 88 8 compound 7 1.00 91

The data in Table H shows that the compounds 1, 7, 11, 35 and 13 of the invention are about 2 times better than that of Tinuvin P in light stabilizing activity.

35 02 4 8 1

Claims (3)

2. Polymeric composition having a stabilizing effect with respect to light, consisting of a polymer and a light stabilizing agent, characterized in that as stabilizer are 2,2,6,6-tetra-methylpiperidylamides of substituted carboxylic acids used according to claim 1 in the following amounts: 99.0-99> 95 parts by weight of polymer and 1.0-0.05 parts by weight of 2,2,6,6-tetramethylpiperidylamide of a substituted carboxylic acid. A photostable polymer composition according to claim 2, characterized in that it further contains a thermo-stabilizing agent in an amount of 0.05 to 0.3% by weight of the polymer. Photostable polymer composition according to claims 20 and 3, characterized in that it further contains a UV light absorbing agent in an amount of 0.1 to 0.3% by weight, based on the polymer. Eindhoven, September 1985 3302481