Oligomeric light stabilizers with a specific functionalization

Abstract

A compound of the formula (I) wherein m and n are independently of one another a number from 1 to 50; the ratio of m/n is 1:10 to 10:1, the recurring units X can have the same definition or different definitions, the recurring units Y can have the same definition or different definitions and the recurring units X and Y can have a random, alternating or block distribution; the recurring unit X is a group of the formula (I-a) and the recurring unit Y is a group of the formula (I-b) the radicals R.sub.1 independently of one another are C.sub.1-C.sub.12alkyl or C.sub.3-C.sub.12cycloalkyl; the radicals R.sub.2 and R.sub.4 are independently of one another C.sub.12-C.sub.30alkyl; the radicals R3 are independently of one another hydrogen, C.sub.1-C.sub.12alkyl or C.sub.3-C.sub.12cycloalkyl. ##STR00001##

Claims

1. A compound of formula (I): ##STR00012## wherein: m and n are independently of one another a number from 1 to 50; the ratio of m/n is 1:10 to 10:1; the recurring units X can have the same definition or different definitions; the recurring units Y can have the same definition or different definitions; and the recurring units X and Y can have a random, alternating or block distribution; the recurring unit X is a group of formula (I-a): ##STR00013## the recurring unit Y is a group of formula (1-b) ##STR00014## the radicals R.sub.1 independently of one another are C.sub.1-C.sub.12alkyl or C.sub.3-C.sub.12cycloalkyl; the radicals R.sub.2 and R.sub.4 are independently of one another C.sub.12-C.sub.30alkyl; and the radicals R.sub.3 are independently of one another hydrogen, C.sub.1-C.sub.12alkyl, or C.sub.3-C.sub.12cycloalkyl.

2. The compound according to claim 1, wherein R.sub.1 is C.sub.1-C.sub.8alkyl or cyclohexyl, R.sub.2 and R.sub.4 are independently of one another C.sub.15-C.sub.24alkyl and R.sub.3 is hydrogen, C.sub.1-C.sub.4alkyl, or cyclohexyl.

3. The compound according to claim 1, wherein R.sub.1 is propyl, R.sub.2 and R.sub.4 are independently of one another C.sub.16-C.sub.22alkyl, and R.sub.3 is hydrogen or methyl.

4. The compound according to claim 1, which corresponds to ##STR00015## wherein the two different recurring units have a random distribution and the ratio of m/n is 1:3 to 3:1.

5. The compound according to claim 1, which corresponds to formula ##STR00016## wherein the two different recurring units have a random distribution and the ratio of m/n is 1:3 to 3:1.

6. A composition comprising A) an organic material subject to degradation induced by light, heat, or oxidation, and B) the compound of the formula (I) as defined in claim 1.

7. The composition according to claim 6, further comprising one, two or more components selected from the group consisting of: (C-1) a filler or reinforcing agent, (C-11) a pigment, (C-111) a further light stabilizer, (C-IV) a processing additive, (C-V) an antioxidant, and (C-VI) a terpene derivative.

8. The composition according to claim 6 wherein component (A) is a thermoplastic natural or synthetic polymer.

9. The composition according to claim 6 wherein component (A) is a polyolefin homo- or copolymer, a starch modified polyolefin or a starch based polymer composite.

10. The composition according to claim 6 wherein component (a) is a polyethylene, a polypropylene, a polyethylene copolymer, or a polypropylene copolymer.

11. A shaped article made of the composition according to claim 6.

12. The shaped article according to claim 11, which is a film, fibre, profile, pipe, bottle, tank, or container.

13. The shaped article according to claim 11, which is a mulch film.

14. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material at least one compound of the formula (I) as defined in claim 1.

15. A compound of formula (II) ##STR00017## wherein z is a number from 1 to 50.

Description

EXAMPLE 1

Preparation of the Compound of the Formula

(1) ##STR00009##
wherein z is 5 to 7.

(2) A 500 ml autoclave equipped with a mechanical stirrer is loaded with 40.0 g of C.sub.20-C.sub.24-alpha-alk-1-ene-maleic acid anhydride copolymer, 28.8 g of 1-n-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine, 300 ml of xylene and 10 ml of acetic acid (100%). The mixture is heated at 140 C. for 6 hours. The obtained product is cooled down at room temperature and the solvent is removed to give a brown solid which is dissolved in 50 ml of CH.sub.2Cl.sub.2 and which is washed several times with a 10% solution of K.sub.2CO.sub.3 in water until pH=7. The organic phase is concentrated at a rotavapor and the obtained polymer is cooled down at 30 C., milled, suspended in cold acetone and stirred for 20 minutes to give a yellow powder which is filtered over a bckner. The desired product is dried in an oven under reduce pressure at 60 C.

(3) Yield: 28 g

(4) TGA (Thermographic Analysis; Air, 10 C./min): 205 C.: 0.21%; 260 C.: 0.69%; 300 C.: 1.27%

(5) FT-IR (Fourier transform infrared spectroscopy): 1700 cm-1: stretching CO imide;

(6) Elemental Analysis: C: 75.8%; H: 11.58%; N: 4.16%; O: 8.07%

(7) Melting point: 43-64 C.

(8) Number Average Molecular weight (Mw): 3000-4000 g/mol

EXAMPLE 2

Preparation of the Compound of the Formula

(9) ##STR00010##
wherein the two different recurring units have a random distribution and are present in about equimolar amounts and m+n is 5 to 7.

(10) A 500 ml autoclave equipped with a mechanical stirrer is loaded with 50.0 g of C.sub.20-C.sub.24-alpha-alk-1-ene-maleic acid anhydride copolymer, 16.51 g of 2,2,6,6-tetramethyl-4-aminopiperidine, 22.7 g of 1-n-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine, 300 ml of xylene and 10 ml of acetic acid (100%). The mixture is heated at 140 C. for 10 hours. The product is cooled down at room temperature and the solvent is removed to give a brown solid which is dissolved in 60 ml of CH.sub.2Cl.sub.2 and which is washed several times with a 10% solution of K.sub.2CO.sub.3 in water until pH=7. The organic phase is concentrated at a rotavapor and the obtained polymer is cooled down at 30 C., milled, suspended in cold acetone and stirred for 20 minutes to give a yellow powder which is filtered over a bckner. The obtained product is dried in an oven under reduce pressure at 60 C.

(11) Yield: 31 g

(12) TGA (Air, 10 C./min): 205 C.: 0.58%; 256 C.: 1.09%; 300 C.: 3.49%

(13) FT-IR: 1700 cm-1: stretching CO imide

(14) Elemental Analysis: C: 74.82%; H: 11.40%; N: 3.96%; O: 6.11%

(15) Melting point: 48-56 C.

(16) Number Average Molecular weight (Mw): 3000-4000 g/mol

EXAMPLE 3

Preparation of the Compound of the Formula

(17) ##STR00011##
wherein the two different recurring units have a random distribution and are present in about equimolar amounts and m+n is 5 to 7.

(18) A 500 ml autoclave equipped with a mechanical stirrer is loaded with 50.0 g of C.sub.20-C.sub.24-alpha-alk-1-ene-maleic acid anhydride copolymer, 18.0 g of 1,2,2,6,6-pentamethyl-4-aminopiperidine, 22.7 g of 1-n-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine, 300 ml of xylene and 10 ml of acetic acid (100%). The mixture is heated at 140 C. for 15 hours. The obtained product is cooled down at room temperature and the solvent is removed to give a brown solid which is dissolved in 60 ml of CH.sub.2Cl.sub.2 and which is washed several times with a 10% solution of K.sub.2CO.sub.3 in water until pH=7. The organic phase is concentrated at a rotavapor and the obtained polymer is cooled down at 30 C., milled, suspended in cold acetone and stirred for 20 minutes to give a yellow-brown powder which is filtered over a bckner. The product is dried in an oven under reduced pressure at 70 C.

(19) Yield: 28 g

(20) TGA (Air, 10 C./min): 210 C.: 0.48%; 260 C.: 2.05%; 300 C.: 3.13%

(21) FT-IR: 1700 cm-1: stretching CO imide

(22) Elemental Analysis: C: 74.65%; H: 12.03%; N: 3.92%; O: 6.03%

(23) Melting point: 44-50 C.

(24) Number average molecular weight (Mw): 3000-4000 g/mol

EXAMPLE A

(25) Film manufacture: In a turbo mixer (Caccia, Labo 10) the additives listed in Table 1 are mixed with LDPE (Low Density Polyethylene) at an overall 10% by weight concentration keeping the 4:1 ratio reported in Table 1. The mixture is extruded at a maximum temperature of 200 C. to granules using an O.M.C. twin-screw extruder (model ebv 19/25). The granules are subsequently mixed and diluted with the same LDPE in order to obtain the final composition for preparing a 150 m thick film, using a blow-extruder (Dolci) working at a maximum temperature of 210 C. The final concentrations of the LDPE films are indicated in Table 1.

(26) TABLE-US-00001 TABLE 1 Final composition of the LDPE films Film No. Additives Film 1 0.4% Compound 1 0.1% of Antioxidans A Film 2 0.4% of Compound 2 0.1% of Antioxidans A Film 3 0.4% of Compound 3 0.1% of Antioxidans A
% means % by weight, relative to the LDPE.
Antioxidans A:

(27) (Irganox 1010)

(28) Tetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionyloxymethyl]methane

(29) Test Methods:

(30) Light exposure: The LDPE films obtained are exposed in an ATLAS Weatherometer (model Ci65A) equipped with a 6500 W Xenon lamp (0.35 W/m.sup.2; continuous light cycle, black panel temperature=63 C.).

(31) Vapam Treatment: The LDPE films obtained are placed in a close chamber and exposed to the vapors of a 0.74 v/v solution of VAPAM (Sodium N-methyldithiocarbamate 39.1 WT %) in water. The final volume is 2000 ml. The system is kept at 30 C. for 20 days. Then, the LDPE films are subjected to light exposure as described above.

(32) Evaluation Parameters:

(33) 1) Carbonyl increment (CO): Evaluation of the carbonyl band increment (1710 cm-1) in function of the exposure time is monitored with a FT-IR Perkin-Elmer Spectrum One.

(34) 2) Tensile elongation @ break: Evaluation of elongation % property is carried out with a ZWICK Z1.0 testing machine: speed: 100 mm/min; holder distance: 30 mm; Temperature: 20 C.

(35) The results are listed in Tables 2 to 4.

(36) TABLE-US-00002 TABLE 2 Carbonyl increment of a 150 m LDPE film after hours (h) of light exposure Carbonyl increment *) 0 h 474 h 1479 h 2490 h 3988 h 4992 h Film 1 0.000 0.007 0.012 0.019 0.044 0.056 Film 2 0.000 0.006 0.018 0.025 0.050 0.065 Film 3 0.000 0.006 0.013 0.015 0.048 0.052 *) Low values are desired.

(37) TABLE-US-00003 TABLE 3 Carbonyl increment of a 150 m LDPE film after hours (h) of light exposure and VAPAM treatment Carbonyl increment *) 0 h 554 h 1451 h 2059 h 2532 Film 1 0.000 0.010 0.028 0.043 0.062 Film 2 0.000 0.018 0.034 0.051 0.067 Film 3 0.000 0.020 0.031 0.049 0.066 *) Low values are desired.

(38) TABLE-US-00004 TABLE 4 Tensile elongation @ break of a 150 m LDPE film after hours (h) of light exposure and VAPAM treatment Tensile elongation @ break **) 0 h 2556 h 3490 h Film 1 100 79 72 Film 2 100 63 50 Film 3 100 73 65 **) High values are desired.