POLYURETHANE FOAM OR POLYETHER POLYOL STABILIZED WITH A BENZOFURANONE-PHOSPHITE DERIVATIVE

Abstract

The invention relates to a composition, which comprises the components (a) a polyurethane foam or a polyether polyol; and (b) a compound of formula (I) wherein R.sup.1 is H or C.sub.1-alkyl. A process for manufacturing the aforementioned composition, the use of a component (b) for stabilizing component (a) against degradation and a specific additive mixture comprising component (b) and as component (c) a first further additive, which is a specific aromatic amine, are described.

##STR00001##

Claims

1. A composition, comprising: (a) a polyurethane foam or a polyether polyol; and (b) a compound of formula I ##STR00026## wherein R.sup.1 is H or C.sub.1-alkyl.

2. The composition according to claim 1, wherein at formula I R.sup.1 is C.sub.1-alkyl.

3. The composition according to claim 1, wherein the polyurethane foam is obtained from the reaction of a polyisocyanate reactant and a polyol reactant in a reaction mixture, and 60 to 100 parts by weight of the polyol reactant based on 100 parts by weight of the polyol reactant is a polyether polyol.

4. The composition according to claim 1, wherein the polyurethane foam is obtained from the reaction of a polyisocyanate reactant and a polyol reactant in a reaction mixture, and the reaction mixture contains prior to the reaction water, a carboxylic acid or a blowing agent.

5. The composition according to claim 1, wherein the polyurethane foam has a density between 5 to 500 kg/m.sup.3 at 20° C. and 101.3 kPa.

6. The composition according to claim 1, wherein component (a) is a polyurethane foam.

7. The composition according to claim 1, wherein the polyurethane foam is obtained from the reaction of a polyisocyanate reactant and a polyol reactant in a reaction mixture, and the amount of component (b) is in case of the polyurethane foam from 0.01 to 2 parts by weight based on 100 parts by weight of the polyol reactant and in case of a polyether polyol from 0.01 to 2 parts by weight based on 100 parts by weight of the polyether polyol.

8. The composition according to claim 1, further comprising: (c) a first further additive.

9. The composition according to claim 8, wherein component (c) is an aromatic amine, a phosphite different to formula I or a phenolic antioxidant.

10. The composition according to claim 9, wherein component (c) is a phenylarylamine with one nitrogen atom, wherein the nitrogen atom is only substituted with a phenyl and an C.sub.6-C.sub.10-aryl and the phenyl or the C.sub.6-C.sub.10-aryl is alkylated, a phosphite, which is an ester of at least one aliphatic alcohol having at least one primary hydroxyl group, or a phenolic antioxidant, which is an ester of 3-(3,5-ditert-butyl-4-hydroxy-phenyl)propanoic acid or an ester of 3-(3-tert-butyl-4-hy-droxy-5-methyl-phenyl)propanoic acid.

11. The composition according to claim 8, further comprising: (d) a second further additive different to the first further additive.

12. The composition according to claim 11, further comprising: (c) a first further additive, and the first further additive is a phenolic antioxidant, and (d) a second further additive, and the second further additive is an aromatic amine or a phosphite different to formula I.

13. The composition according to claim 12, further comprising: (c) a first further additive, wherein the first further additive is a phenolic antioxidant, which is an ester of 3-(3,5-ditert-butyl-4-hydroxy-phenyl)propanoic acid or an ester of 3-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)propanoic acid, and (d) a second further additive, wherein the second further additive is a phenylarylamine with one nitrogen atom, wherein the nitrogen atom is only substituted with a phenyl and an C.sub.6-C.sub.10-aryl and the phenyl or the C.sub.6-C.sub.10-aryl is alkylated, or a phosphite, which is an ester of at least one aliphatic alcohol having at least one primary hydroxyl group.

14. The composition according to claim 8, wherein the weight ratio between component (b) and component (c) is from 0.08 to 2.

15. The composition according to claim 11, wherein the weight ratio between component (b) and component (d) is from 0.5 to 2.

16. A process for manufacturing the composition of claim 1, the process comprising: (i) incorporating a compound of formula (I) as component (b) into the polyurethane foam or the polyether polyol as component (a) to obtain the composition.

17. A method of using a compound of formula I as component (b) for protecting a polyurethane foam or a polyether polyol as component (a) against degradation, wherein the compound of formula I has the following structure: ##STR00027## wherein R.sup.1 is H or C.sub.1-alkyl.

18. An additive mixture, comprising: (b) a compound of formula I ##STR00028## wherein R.sup.1 is H or C.sub.1-alkyl, and (c) a first further additive comprising a phenylarylamine with one nitrogen atom, wherein the nitrogen atom is only substituted with a phenyl and an C.sub.6-C.sub.10-aryl and the phenyl or the C.sub.6-C.sub.10-aryl is alkylated.

Description

EXPERIMENTAL PART

[0230] Unless the context suggests otherwise, percentages are always by weight. A reported content is based on the content in aqueous solution or dispersion if not stated otherwise.

[0231] Stabilizers

[0232] Stabilizer 1 is compound (101) as depicted below and obtainable according to example S-3 of WO 2015/121445 A1.

##STR00009##

[0233] Stabilizer 2 is compound (102) as depicted below and obtainable according to example S-5 of WO 2015/121445 A1.

##STR00010##

[0234] Stabilizer 3 is compound (103) as depicted below and obtainable according to example S-7 of WO 2015/121445 A1.

##STR00011##

[0235] Stabilizer 4 is compound (104) as depicted below and obtainable according to example S-8 of WO 2015/121445 A1.

##STR00012##

[0236] Stabilizer 5 is compound (105) as depicted below and obtainable according to example P-2 of WO 2017/025431 A1.

##STR00013##

[0237] Stabilizer 6 is compound (106) as depicted below and obtainable according to EP 0871066 A1 with its compound No. 1-30.

##STR00014##

[0238] Stabilizer 7 is the product of a reaction of 5,7-ditert-butyl-3-[4-(2-hydroxyethoxy)phenyl]-3H-benzofuran-2-one and of ε-caprolactone, contains compound (107) as depicted below and is obtainable according to example 3 of WO 2006/065829 A1.

##STR00015##

[0239] Stabilizer 8 is the product of a transesterification of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid methyl ester with polyethylene glycol 200, contains compound (108) as depicted below and is obtainable according to example 1a of WO 2010/003813 A1.

##STR00016##

[0240] Stabilizer 9 is Irganox 245 (TM BASF), which contains compound (109) as depicted below and is commercially obtainable.

##STR00017##

[0241] Stabilizer 10 is Irganox E 201 (TM BASF), which is a commercially available vitamin E and contains compound (110) [=2,5,7,8-tetramethyl-2-[4,8,12-trimethyltridecyl]chroman-6-ol] as depicted below.

##STR00018##

[0242] Stabilizer 11 is Irganox 1010 (TM BASF), which contains compound (111) as depicted below and is commercially available.

##STR00019##

[0243] Stabilizer 12 is Irganox 1135 (TM BASF), which contains compound (112) [=3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionic acid iso-octyl ester] as depicted below and is commercially available.

##STR00020##

[0244] Stabilizer 13 is Irganox 1076 (TM BASF), which contains compound (113) as depicted below and is commercially available.

##STR00021##

[0245] Stabilizer 14 is Irganox 5057 (TM BASF), which is a technical mixture obtained by the reaction of diphenylamine with diisobutylene, comprising [0246] (A).sub.5057 diphenylamine; [0247] (B).sub.5057 4-tert-butyldiphenylamine; [0248] (C).sub.5057 compounds of the group [0249] i) 4-tert-octyldiphenylamine, [0250] ii) 4,4′-di-tert-butyldiphenylamine, [0251] iii) 2,4,4′-tris-tert-butyldiphenylamine, [0252] (D).sub.5057 compounds of the group [0253] i) 4-tert-butyl-4′-tert-octyldiphenylamine, [0254] ii) o,o′, m,m′, or p,p′-di-tert-octyldiphenylamine, [0255] iii) 2,4-di-tert-butyl-4′-tert-octyldiphenylamine, [0256] (E).sub.5057 compounds of the group [0257] i) 4,4′-di-tert-octyldiphenylamine, [0258] ii) 2,4-di-tert-octyl-4′-tert-butyldiphenylamine, and
wherein not more than 5% by weight of component (A).sub.5057, 8 to 15% by weight of component (B).sub.5057, 24 to 32% by weight of component (C).sub.5057, 23 to 34% by weight of component (D).sub.5057 and 21 to 34% by weight of component (E).sub.5057 are present. It is commercially available.

[0259] Stabilizer 15 is Irganox L06 (TM BASF), which contains compound (115) [═N-[(1,1,3,3-tetramethylbutyl)phenyl]-1-napthalenamine] as depicted below and is commercially available.

##STR00022##

[0260] Stabilizer 16 is Irgafos 126 (TM BASF), which contains compound (116) and is commercially available.

##STR00023##

[0261] The other used materials are commercially available for example from Aldrich Inc. or BASF SE.

[0262] Stabilizer 17 is Irgafos 168 (TM BASF), which contains compound (117) and is commercially available.

##STR00024##

Application

Example A-1: Stabilization of a Polyurethane Soft Foam Based on a Polyether Polyol

[0263] Preparation of polyurethane soft foams based on a polyether polyol with 4.8 parts water based on 100 parts polyol and an isocyanate index of 107 (isocyanate index meaning herein 100 times the ratio between isocyanate equivalents and active hydrogen equivalents in the polyol and water with index 100 indicating a stoichiometry 1 to 1 and with index 107 indicating a 7% excess of isocyanate equivalents):

[0264] 0.05 g of stabilizer product according to the invention as described in table T-A-1 (0.03 parts based on 100 parts of polyol) are dissolved in 157.1 g of a trifunctional polyether polyol predominantly containing secondary hydroxyl groups, with a number average molecular weight (M.sub.n) of 3500 D, with an OH Number of 48 and containing already stabilizers (0.386 parts stabilizer 12 and 0.104 parts stabilizer 14). 9.84 g of a solution consisting of 1.92 g Tegostab BF 2370 (TM Evonik Industries; surfactant based on polysiloxane), 0.24 g Tegoamin 33 (TM Evonik Industries; general purpose gelling catalyst based on triethylene diamine) and 7.68 g of deionized water are added and the reaction mixture is stirred vigorously for 10 seconds at 2600 rpm. 0.31 g Kosmos 29 (TM Evonik Industries; catalyst based on stannous octoate) dissolved with 2.9 g of the polyol are then added and the reaction mixture is again stirred vigorously for 18 seconds at 2600 rpm. 92.19 g of isocyanate TDI 80 (mixture containing 80% toluylene-2,4-diisocyanate and 20% toluylene-2,6-diisocyanate isomers) 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 cake-box and an exothermic foaming reaction takes place as indicated by an increase of temperature. The foam buns are cooled and stored at room temperature for 24 hours. All prepared foam buns show a comparable initial white colour. The density of the foam is 20 kg/m.sup.3 at 20° C. and 101.3 kPa.

[0265] Anti-Scorch Testing:

[0266] Scorch resistance is determined by static heat aging, i.e. static Alu-block test. The foam buns are cut into thin tubes (2 cm thick, 1.5 cm in diameter). From each foam bun, a thin tube is taken as a foam sample. The foam sample is heated in an aluminum block. The temperature is kept for 30 min at the temperature of 190° C. The scorch resistance is assessed by measuring the colour of the foam sample after aging. The measured colour is reported in terms of Yellowness Index (YI) determined on the foam sample in accordance with the ASTM 1926-70 Yellowness Test. Low YI values denote little discoloration, high YI values severe discoloration of the samples. The whiter a foam sample remains, the better the foam sample is stabilized.

TABLE-US-00001 TABLE T-A-1 Results of static Alu-block ageing of polyurethane soft foams stabilizer composition overall YI after 30 Foam (parts based on 100 parts of min exposure No. parts polyether polyol) stabilizer at 190° C. A-1-1 .sup.a) 0.386 parts of stabilizer 12 0.49 11 0.104 parts of stabilizer 14 A-1-2 .sup.a) 0.386 parts of stabilizer 12 0.52 10.6 0.104 parts of stabilizer 14 0.03 parts of stabilizer 1 A-1-3 .sup.a) 0.386 parts of stabilizer 12 0.52 7.7 0.104 parts of stabilizer 14 0.03 parts of stabilizer 2 A-1-4 .sup.b) 0.386 parts of stabilizer 12 0.52 2.5 0.104 parts of stabilizer 14 0.03 parts of stabilizer 3 A-1-5 .sup.b) 0.386 parts of stabilizer 12 0.52 2.4 0.104 parts of stabilizer 14 0.03 parts of stabilizer 4 A-1-6 .sup.a) 0.386 parts of stabilizer 12 0.52 9.2 0.104 parts of stabilizer 14 0.03 parts of stabilizer 6 .sup.c) Footnotes: .sup.a) comparative .sup.b) according to the invention .sup.c) stabilizer 6 is a benzofuranone substituted with an acetoxy-substituted phenyl, which is applied in example 1 of EP 1291384 A1 for stabilization of a polyurethane soft foam based on a polyether polyol

[0267] The data of table T-A-1 show that stabilizer 3 (a specific mono-benzofuranone phosphite) and stabilizer 4 (a specific mono-benzofuranone phosphite) show an improved anti-scorch activity in comparison to no additional stabilizer, to stabilizer 1 (a specific tris-benzofuranone phosphite), to stabilizer 2 (a specific mono-benzofuranone phosphite) and to stabilizer 6 (a benzofuranone substituted with an acetoxy-substituted phenyl), when added to stabilizer 12 (a mono-phenolic antioxidant) and stabilizer 14 (an alkylated diphenyl amine). Foam sample A-1-5 shows the lowest discoloration, which indicates that the stabilizer 4 gives the highest anti-scorch performance.

Example A-2: Stabilization of a Polyurethane Soft Foam Based on a Polyether Polyol

[0268] Preparation of polyurethane soft foams based on a polyether polyol with 7 parts water based on 100 parts polyol and an isocyanate index 110 (meaning of index as described at example A-1): 0.12 g or 1.20 g of a stabilizer composition (0.1-1 parts based on 100 parts of polyol) according to the invention are dissolved in 108.35 g of a trifunctional polyether polyol predominantly containing secondary hydroxyl groups, with a number average molecular weight (M.sub.r) of 3500 D, with an OH Number of 48 and containing no stabilizers. 10.07 g of a solution consisting of 2.20 g Tegostab BF 2370 (TM Evonik Industries; surfactant based on polysiloxane), 0.17 g Tegoamin 33 (TM Evonik Industries; general purpose gelling catalyst based on triethylenediamine) and 7.7 g of deionized water are added and the reaction mixture is stirred vigorously for 10 seconds at 2600 rpm. 0.33 g Kosmos 29 (TM Evonik Industries; catalyst based on stannous octoate) dissolved with 1.65 g of the polyol are then added and the reaction mixture is again stirred vigorously for 18 seconds at 2600 rpm. 90.86 g of isocyanate TDI80 (mixture containing 80% toluylene-2,4-diisocyanate and 20% toluylene-2,6-diisocyanate isomers) 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 cake-box and an exothermic foaming reaction takes place as indicated by an increase of temperature. The foam buns are cooled down and stored at room temperature for 24 hours. All prepared foam buns show a comparable initial whit colour. The density of the foam is 16 kg/m.sup.3 at 2° C. and 101.3 kPa.

TABLE-US-00002 TABLE T-A-2 Results of static Alu-block ageing of polyurethane soft foams stabilizer composition overall YI after 30 Foam (parts based on 100 parts of min exposure No. parts polyether polyol) stabilizer at 190° C. A-2-1 .sup.a) no stabilizer added — 21.7 A-2-2 .sup.a) 0.1 parts of stabilizer 6 .sup.c) 0.1 8.9 A-2-3 .sup.b) 0.1 parts of stabilizer 4 0.1 8.0 A-2-4 .sup.a) 0.1 parts of stabilizer 7 .sup.d) 0.1 15.3 A-2-5 .sup.a) 0.1 parts of stabilizer 5 0.1 8.9 A-2-6 .sup.a)   1 part of stabilizer 6 .sup.c) 1 6.1 A-2-7 .sup.b)   1 part of stabilizer 4 1 3.3 A-2-8 .sup.a)   1 part of stabilizer 7 .sup.d) 1 4.5 A-2-9 .sup.a)   1 part of stabilizer 5 1 3.7 Footnotes: .sup.a) comparative .sup.b) according to the invention .sup.c) stabilizer 6 is a benzofuranone substituted with an acetoxy-substituted phenyl, which is applied in example 1 of EP 1291384 A1 for stabilization of a polyurethane soft foam based on a polyether polyol .sup.d) stabilizer 7 is a benzofuranone substituted with an alkoxy-substituted phenyl, which is applied in examples of WO 2006/065829 A1 for stabilization of a polyurethane soft foam based on a polyether polyol

[0269] The data of table T-A-2 show that stabilizer 4 (a specific mono-benzofuranone phosphite) shows an anti-scorch activity already in the absence of additional stabilizers. When the loading is increased from 0.1 parts based on 100 parts of polyol towards 1 part based on 100 parts of polyol, stabilizer 4 gives still the highest anti-scorch performance in the present comparison.

Example A-3: Stabilization of a Polyurethane Soft Foam Based on a Polyether Polyol

[0270] Preparation of polyurethane soft foams based on a polyether polyol with 4.8 parts water based on 100 parts polyol and an isocyanate index 107 (meaning of index as described at example A1): 0.16 g of stabilizer 4 (0.1 parts based on 100 parts of polyol) as described in table T-A-3 is dissolved in 157.1 g of a trifunctional polyether polyol predominantly containing secondary hydroxyl groups, with a number average molecular weight (M.sub.n) of 3500 D, with an OH Number of 48 and containing no stabilizers. For foam No. A-3-1, no stabilizer 4 is added. For foams No. A-3-3 to A-3-9, 0.08 g of stabilizer 4 (0.05 parts based on 100 parts of polyol) is added. 9.84 g of a solution consisting of 1.92 g Tegostab BF 2370 (TM Evonik Industries; surfactant based on polysiloxane), 0.24 g Tegoamin 33 (TM Evonik Industries; general purpose gelling catalyst based on triethylene diamine) and 7.68 g of deionized water are added and the reaction mixture is stirred vigorously for 10 seconds at 2600 rpm. 0.31 g Kosmos 29 (TM Evonik Industries; catalyst based on stannous octoate) dissolved with 2.9 g of the polyol are then added and the reaction mixture is again stirred vigorously for 18 seconds at 2600 rpm. 92.19 g of isocyanate TDI 80 (mixture containing 80% toluylene-2,4-diisocyanate and 20% toluylene-2,6-diisocyanate isomers) 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 cake-box and an exothermic foaming reaction takes place as indicated by an increase of temperature. The foam buns are cooled and stored at room temperature for 24 hours. All prepared foam buns show a comparable initial white colour. The density of the foam is 20 kg/m.sup.3 at 20° C. and 101.3 kPa.

TABLE-US-00003 TABLE T-A-3 Results of static Alu-block ageing of polyurethane soft foams stabilizer composition overall YI after 30 Foam (parts based on 100 parts of min exposure No. parts polyether polyol) stabilizer at 190° C. A-3-1 .sup.a) no stabilizer added — 29.5 A-3-2 .sup.b) 0.1 parts of stabilizer 4 0.1 10 A-3-3 .sup.b) 0.05 parts of stabilizer 4  0.1 8.5 0.05 parts of stabilizer 14 A-3-4 .sup.b) 0.05 parts of stabilizer 4  0.1 6.8 0.05 parts of stabilizer 15 A-3-5 .sup.b) 0.05 parts of stabilizer 4  0.45 3.1 0.40 parts of stabilizer 8  A-3-6 .sup.b) 0.05 parts of stabilizer 4  0.45 4.1 0.40 parts of stabilizer 11 A-3-7 .sup.b) 0.05 parts of stabilizer 4  0.45 3.2 0.40 parts of stabilizer 13 A-3-8 .sup.b) 0.05 parts of stabilizer 4  0.45 3.2 0.40 parts of stabilizer 12 A-3-9 .sup.b) 0.05 parts of stabilizer 4  0.45 4.8 0.40 parts of stabilizer 9  Footnotes: .sup.a) comparative .sup.b) according to the invention

[0271] The data of table T-A-3 show that a combination of stabilizer 4 (a specific mono-benzofuranone phosphite) with stabilizer 14 (an alkylated diphenylamine) or stabilizer 15 (an alkylated naphthylphenylamine) reduces scorch discoloration even further than by the same amount of only stabilizer 4. The data of table T-A-3 show further that a combination of stabilizer 4 (a specific mono-benzofuranone phosphite) and stabilizer 8 (a bis-phenolic antioxidant), stabilizer 9 (a bisphenolic antioxidant), stabilizer 11 (a tetrakis-phenolic antioxidant), stabilizer 12 (a mono-phenolic antioxidant) or stabilizer 13 (a mono-phenolic antioxidant) reduces discoloration to an extent dependent on the phenolic antioxidant.

Example A-4: Stabilization of a Polyurethane Soft Foam Based on a Polyether Polyol

[0272] Preparation of polyurethane soft foams based on a polyether polyol with 7 parts water based on 100 parts polyol and an isocyanate index 110 (meaning of index as described at example A-1): 0.54 g of a stabilizer composition (0.45 parts based on 100 parts of polyol) as described in table T-A-4 are dissolved in 108.35 g of a trifunctional polyether polyol predominantly containing secondary hydroxyl groups, with a number average molecular weight of 3500 D, with an OH Number of 48 and containing no stabilizers. For foam No. A-3-1, no stabilizer is added. 10.07 g of a solution consisting of 2.20 g Tegostab BF2370 (TM Evonik Industries; surfactant based on polysiloxane), 0.17 Tegoamin 33 (TM Evonik Industries; general purpose gelling catalyst based on triethylene diamine) and 7.7 g of deionized water are added and the reaction mixture is stirred vigorously for 10 seconds at 2600 rpm. 0.33 g Kosmos 29 (TM Evonik Industries; catalyst based on stannous octoate) dissolved with 1.65 g of the polyol are then added and the reaction mixture is again stirred vigorously for 18 seconds at 2600 rpm. 90.86 g of isocyanate TDI 80 (mixture containing 80% toluylene-2,4-diisocyanate and 20% toluylene-2,6-diisocyanate isomers) is then added with continuous stirring for 5 to 7 seconds at 2600 rpm. The mixture is then poured into a20×20×20 cm cake-box and an exothermic foaming reaction takes place as indicated by an increase of temperature. The foam buns are cooled down and stored at room temperature for 24 hours. All prepared foam buns show a comparable initial white colour. The density of the foam is 16 kg/m.sup.3 at 20° C. and 101.3 kPa.

TABLE-US-00004 TABLE T-A-4 Results of static Alu-block ageing of polyurethane soft foams stabilizer composition overall YI after 30 Foam (parts based on 100 parts of min exposure No. parts polyether polyol) stabilizer at 190° C. A-4-1 .sup.a) no stabilizer added — 29.5 A-4-2 .sup.b) 0.35 parts of stabilizer 8 0.45 6.3  0.05 parts of stabilizer 10 0.05 parts of stabilizer 4 A-4-3 .sup.b) 0.35 parts stabilizer 8 0.45 3.6  0.05 parts of stabilizer 15 0.05 parts of stabilizer 4 A-4-4 .sup.b) 0.35 parts of stabilizer 8 0.45 2.7  0.05 parts of stabilizer 16 0.05 parts of stabilizer 4 A-4-5 .sup.b)  0.35 parts of stabilizer 13 0.45 3.1  0.05 parts of stabilizer 16 0.05 parts of stabilizer 4 A-4-6 .sup.b) 0.320 parts of stabilizer 12 0.45 2.9 0.096 parts of stabilizer 14 0.032 parts of stabilizer 4  A-4-7 .sup.b) 0.320 parts of stabilizer 8  0.45 3.9 0.096 parts of stabilizer 14 0.032 parts of stabilizer 4  Footnotes: .sup.a) comparative .sup.b) according to the invention

[0273] The data of table T-A-4 show that ternary combinations including stabilizer 4 (a specific mono-benzofuranone phosphite) provide anti-scorch performance.

Example A-5: Stabilization of a Polyether Polyol

[0274] Preparation of a Stabilized Polyether Polyol:

[0275] 0.45 g of a composition of stabilizers (0.45 parts based on 100 parts of polyol) as depicted in table T-A-5 are dissolved in 100 g of a trifunctional polyether polyol predominantly containing secondary hydroxyl groups, with a number average molecular weight (M.sub.r) of 3500 D, with an OH number of 48 and containing no stabilizer.

[0276] Oxidation Resistance Testing:

[0277] The oxidation resistance of an obtained stabilized polyether polyol sample is determined by differential scanning calorimetry (DSC). The sample is heated starting at 50′C with a heating rate of 5° C./min under oxygen until 200° C. is reached. The appearance of an exothermic peak indicates the beginning of a thermo-oxidative reaction. The temperature at the onset of the exothermic peak is noted. A better stabilized sample is characterized by a higher temperature for the onset. The results are depicted in table T-A-5.

TABLE-US-00005 TABLE T-A-5 Results of oxidation resistance testing of stabilized polyether polyols stabilizer composition overall onset Foam (parts based on 100 parts of temperature No. parts polyether polyol) stabilizer [° C.] A-5-1 .sup.b) 0.35 parts of stabilizer 8 0.45 201  0.05 parts of stabilizer 10 0.05 parts of stabilizer 4 A-5-2 .sup.b) 0.35 parts stabilizer 8 0.45 189  0.05 parts of stabilizer 15 0.05 parts of stabilizer 4 A-5-3 .sup.b) 0.35 parts of stabilizer 8 0.45 189  0.05 parts of stabilizer 16 0.05 parts of stabilizer 4 A-5-4 .sup.b)  0.35 parts of stabilizer 13 0.45 183  0.05 parts of stabilizer 16 0.05 parts of stabilizer 4 A-5-5 .sup.b) 0.320 parts of stabilizer 12 0.45 197 0.096 parts of stabilizer 14 0.032 parts of stabilizer 4  A-5-6 .sup.b) 0.320 parts of stabilizer 8  0.45 198 0.096 parts of stabilizer 14 0.032 parts of stabilizer 4  Footnotes: .sup.a) comparative .sup.b) according to the invention

[0278] The data of table T-A-5 show that ternary combinations comprising stabilizer 4 (a specific mono-benzofuranone phosphite) stabilize the polyether polyol.

Example A-6: Stabilization of a Molded Thermoplastic Polyurethane Based on a Polyether Polyol

[0279] Preparation of Molded Thermoplastic Polyurethane Test Panels (Plaques)

[0280] Compounding

[0281] 3.0 kg of a commercial thermoplastic polyurethane (TPU, based on an aliphatic polyether polyol, extrusion and injection molding grade, shore D value of 55, with a content of 0.25 parts by weight of stabilizer 11 and 0.05 parts by weight of stabilizer 17, each weight parts based on 100 parts of thermoplastic polyurethane, in the physical form of pellets) are ground in a cryogenic mill and dried under vacuum at 80° C. until water content is below 0.05% by weight of the thermoplastic polyurethane. The obtained powder is mixed to homogeneity in a tumbler mixer after addition of 0.05 parts by weight of a further stabilizer according to table T-A-6-1/T-A-6-2 or no additional stabilizer for reference. The obtained blend is then immediately extruded in a twin-screw extruder Berstorff ZE 25×32D (TM Berstorff) at a temperature of at most 220° C. The obtained granulate is dried again under dry air at 80° C. until the water content is below to 0.03% by weight of the granules.

[0282] Injection Molding

[0283] Test panels (plaques) of the size 64 mm×44 mm×2 mm are molded from the obtained granulates by means of an injection-molding machine, i.e. an Engel HL 60 (TM Engel), at a temperature of at most 230° C. (mold temperature: 40° C.). The density of the test panels (plaques) is 1170 kg/m.sup.3 (1.17 g/cm.sup.3) at 20° C. and 101.3 kPa.

[0284] Thermo-Oxidation Resistance Test

[0285] The thermo-oxidation resistance of the manufactured thermoplastic polyurethane test panels is tested by putting them in an air-circulating oven at the temperature of 120° C. A plaque's initial color before heat ageing and its discoloration after exposure in the oven is measured and compared. Results are depicted in table T-A-6-1.

[0286] Accelerated Weathering Resistance Test

[0287] The light stability and accelerated weathering resistance of the manufactured thermoplastic polyurethane test panels is tested by exposing them in a Weather-Ometer Ci4000 (TM Atlas) according to the standard D27-1911. The surface discoloration is then measured (Delta E). Results are described in table T-A-6-2.

TABLE-US-00006 TABLE T-A-6-1 Results of thermo-oxidation resistance test stabilizer composition delta E after Test panel (parts based on 100 parts oven ageing at No. molded polyurethane) 120° C. for 48 h A-6-1-1 .sup.a) 0.25 parts of stabilizer 11 .sup.b) 3.04 0.05 parts of stabilizer 17 .sup.b) A-6-1-2 .sup.a) 0.25 parts of stabilizer 11 .sup.b) 3.02 0.05 parts of stabilizer 17 .sup.b) 0.05 parts of stabilizer 6 .sup.c), d) A-6-1-3 .sup.a) 0.25 parts of stabilizer 11 .sup.b) 3.48 0.05 parts of stabilizer 17 .sup.b) 0.05 parts of stabilizer 7 .sup.c), e) A-6-1-4 .sup.a) 0.35 parts of stabilizer 11 .sup.b) 2.97 0.05 parts of stabilizer 17 .sup.b) 0.05 parts of stabilizer 4 .sup.c) Footnotes: .sup.a) comparative .sup.b) contained prior compounding .sup.c) added during compounding .sup.d) stabilizer 6 is a benzofuranone substituted with an acetoxy-substituted phenyl, which is applied in example 1 of EP 1291384 A1 for stabilization of a polyurethane soft foam based on a polyether polyol .sup.e) stabilizer 7 is a benzofuranone substituted with an alkoxy-substituted phenyl, which is applied in examples of WO 2006/065829 A1 for stabilization of a polyurethane soft foam based on a polyether polyol

TABLE-US-00007 TABLE T-A-6-2 Results of accelerated weathering resistance test stabilizer composition delta E after exposure Test panel (parts based on 100 parts to D27-1911 for No. molded polyurethane) 1179 h 1522 h 2016 h A-6-2-1 .sup.a) 0.25 parts of stabilizer 11 .sup.b) 9.89 10.59 9.77 0.05 parts of stabilizer 17 .sup.b) A-6-2-2 .sup.a) 0.25 parts of stabilizer 11 .sup.b) 9.08 9.57 8.14 0.05 parts of stabilizer 17 .sup.b) 0.05 parts of stabilizer 6 .sup.c), d) A-6-2-3 .sup.a) 0.25 parts of stabilizer 11 .sup.b) 9.85 10.06 9.62 0.05 parts of stabilizer 17 .sup.b) 0.05 parts of stabilizer 7 .sup.c), e) A-6-2-4 .sup.a) 0.35 parts of stabilizer 11 .sup.b) 9.23 9.62 9.25 0.05 parts of stabilizer 17 .sup.b) 0.05 parts of stabilizer 4 .sup.c) Footnotes: see footnotes at table T-A-6-1

[0288] The data of tables T-A-6-1 and T-A-6-2 show that stabilizer 4 (a specific mono-benzofuranone phosphite) is better than stabilizer 6 (a benzofuranone substituted with an acetoxy-substituted phenyl) at the thermo-oxidation resistance test of the molded polyurethane test panel, whereas stabilizer 4 is worse than stabilizer 6 at the accelerated weathering resistance test of the molded polyurethane test panel. Both testings occur in the presence of stabilizer 11 (a tetrakis-phenolic antioxidant) and stabilizer 11 (a phosphite, which is an ester without an aliphatic alcohol). Stabilizer 7 (a benzofuranone substituted with an alkoxy-substituted phenyl) is inferior to stabilizer 4 and stabilizer 6 in both testings. These results show that the performance difference between stabilizer 4 and stabilizer 6 in a polyurethane foam is not seen in a molded thermoplastic polyurethane test panel.

[0289] Preferred is the following set of clauses 1 to 19:

[0290] 1. A composition, which comprises the components [0291] (a) a polyurethane foam; and [0292] (b) a compound of formula I

##STR00025## [0293] wherein R.sup.1 is H or methyl.

[0294] 2. A composition according to clause 1, wherein the composition is in the form of a shaped article.

[0295] 3. A composition according to clause 1 or 2, wherein at formula I R.sup.1 is methyl.

[0296] 4. A composition according to any preceding clause, wherein the polyurethane foam is obtained from the reaction of a polyisocyanate reactant and a polyol reactant in a reaction mixture, and 60 to 100 parts by weight of the polyol reactant based on 100 parts by weight of the polyol reactant is a polyether polyol.

[0297] 5. A composition to any preceding clause, wherein the polyurethane foam is obtained from the reaction of a polyisocyanate reactant and a polyol reactant in a reaction mixture, and the reaction mixture contains prior to the reaction water, a carboxylic acid or a blowing agent.

[0298] 6. A composition according to any preceding clause, wherein the polyurethane foam has a density between 5 to 500 kg/m.sup.3 at 20° C. and 101.3 kPa.

[0299] 7. A composition according to any preceding clause, wherein the composition is a foam.

[0300] 8. A composition according to any preceding clause, wherein the polyurethane foam is obtained from the reaction of a polyisocyanate reactant and a polyol reactant in a reaction mixture, and the amount of component (b) is from 0.01 to 2 parts by weight based on 100 parts by weight of the polyol reactant.

[0301] 9. A composition according to any preceding clause, which comprises additionally [0302] (c) a first further additive.

[0303] 10. A composition according to clause 9, wherein component (c) is an aromatic amine, a phosphite different to formula I or a phenolic antioxidant.

[0304] 11. A composition according to clause 10, wherein component (c) is a phenylarylamine with one nitrogen atom, wherein the nitrogen atom is only substituted with a phenyl and an C.sub.6-C.sub.10-aryl and the phenyl or the C.sub.6-C.sub.10-aryl is alkylated, a phosphite, which is an ester of at least one aliphatic alcohol having at least one primary hydroxyl group, or a phenolic antioxidant, which is an ester of 3-(3,5-ditert-butyl-4-hydroxy-phenyl)propanoic acid or an ester of 3-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)propanoic acid.

[0305] 12. A composition according to anyone of clauses 9 to 11, which comprises additionally [0306] (d) a second further additive, which is different to the first further additive.

[0307] 13. A composition according to clause 12, which comprises [0308] (c) a first further additive, and the first further additive is a phenolic antioxidant, and [0309] (d) a second further additive, and the second further additive is an aromatic amine or a phosphite different to formula I.

[0310] 14. A composition according to clause 13, which comprises [0311] (c) a first further additive, and the first further additive is a phenolic antioxidant, which is an ester of 3-(3,5-ditert-butyl-4-hydroxy-phenyl)propanoic acid or an ester of 3-(3-tertbutyl-4-hydroxy-5-methyl-phenyl)propanoic acid, and [0312] (d) a second further additive, and the second further additive is a phenylarylamine with one nitrogen atom, wherein the nitrogen atom is only substituted with a phenyl and an C.sub.6-C.sub.10-aryl and the phenyl or the C.sub.6-C.sub.10-aryl is alkylated, or a phosphite, which is an ester of at least one aliphatic alcohol having at least one primary hydroxyl group.

[0313] 15. A composition according to anyone of clauses 9 to 14, wherein the weight ratio between component (b) and component (c) is from 0.08 to 2.

[0314] 16. A composition according to anyone of clauses 12 to 15, wherein the weight ratio between component (b) and component (d) is from 0.5 to 2.

[0315] 17. A process for manufacturing a composition as defined in anyone of clauses 1 to 16, which comprises the step of [0316] (i) incorporating a compound of formula (I) as defined in clause 1 as component (b) into a polyurethane foam as defined in clause 1 as component (a) to obtain the composition.

[0317] 18. Use of a compound of formula I as defined in clause 1 as component (b) for protecting a polyurethane foam as defined in clause 1 as component (a) against degradation.

[0318] 19. An additive mixture, which comprises the components [0319] (b) a compound of formula I as defined in clause 1, and [0320] (c) a first further additive, which is a phenylarylamine with one nitrogen atom, wherein the nitrogen atom is only substituted with a phenyl and an C.sub.6-C.sub.10-aryl and the phenyl or the C.sub.6-C.sub.10-aryl is alkylated.