Stabilized copolyesterether compositions suitable for outdoor applications

• US 4,524,165 A
• Filed: 10/24/1983
• Issued: 06/18/1985
• Est. Priority Date: 10/24/1983
• Status: Expired due to Term

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Kodak Company
• Inventors: Musser, Harry R., Zannucci, Joseph S., Strickland, Thomas H.
• Primary Examiner(s): Kight, John
• Assistant Examiner(s): SANDERS, KRIELLION ANTIONETTE
• Application Number:
  US06/544,035
• Time in Patent Office: 603 Days
• Field of Search: 524/99, 524/101, 524/102, 524/103, 524/208, 524/220, 524/222, 524/259, 524/291, 524/335, 524/336, 524/337, 524/338, 524/357, 528/272, 528/302, 528/307, 525/437, 525/448
• US Class Current: 524/99
• CPC Class Codes: C08K 5/00 Use of organic ingredients
• CPC Class Codes: C08K 5/3435 Piperidines
• CPC Class Codes: C08K 5/3462 Six-membered rings
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence

Abstract

Disclosed are stabilized polyester compositions having significantly improved weatherability. These polyesters consist of copolyesterethers derived from a dicarboxylic acid component comprising about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second dicarboxylic acid and a glycol component comprising about 70-95 mole % 1,4-cyclohexanedimethanol and about 5-30 mole % of a polyalkylene ether glycol having a molecular weight of about 600 to about 3000. The copolyesterether compositions further comprise a stabilizing effective amount of the combination of (1) at least one hindered phenolic antioxidant, (2) at least one ultraviolet light stabilizing compound compatible with said copolyesterether and (3) at least one hindered amine light stabilizing compound having the formulae ##STR1## the groups shown as R¹, R², R³ and R⁴ are each independently selected from various substituents.

Claims

1. A highly weatherable copolyesterether composition having a 264 psi heat deflection temperature greater than 60°

C. and an inherent viscosity of about 0.8 to about 1.5, said copolyesterether comprising

A. a 100 mole % dicarboxylic acid component comprising about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second acid selected from the group consisting of aliphatic dicarboxylic acids having 3 to 12 carbon atoms,

B. a 100 mole % glycol component comprising about 70-95 mole % 1,4-cyclohexanedimethanol and about 5-30 mole % of a polyalkylene ether glycol having a molecular weight of about 600 to about 3000,

C. a stabilizing effective amount of the combination of

1. at least one hindered phenolic antioxidant,

2. at least one ultraviolet light stabilizing compound compatible with said copolyesterether, and

3. at least one hindered amine light stabilizing compound having the formulae ##STR4## wherein m and n are each integers of from 1 to 20, R¹, R², R³ and R⁴ are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 22 carbon atoms, alkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 12 carbon atoms, hydroxyalkyl having 1 to 18 carbon atoms, and esters of said hydroxyalkyl; and

alkylenecarboxylic acid having 2 to 18 carbon atoms and esters, amides and metal salts of said alkylenecarboxylic acid.

2. A copolyesterether composition according to claim 1 wherein said phenolic antioxidant is present in an amount of about 0.01 to about 1.0 weight %, said ultraviolet light stabilizing compound is present in an amount of about 0.05 to about 5.0 weight % and said hindered amine light stabilizing compound is present in an amount of about 0.05 to about 2.0 weight %, based on the weight of said copolyesterether.

3. A copolyesterether composition according to claim 1 wherein said ultraviolet light stabilizing compound is selected from the group consisting of a compound having the formula ##STR5## wherein R⁵, R⁶, and R⁷ are each independently selected from hydrogen, hydroxyl, branched or unbranched, substituted or unsubstituted alkyl or alkoxy radicals containing from 1 to 18 carbon atoms, aryl, and alkylenearyl containing from 7 to 22 carbon atoms;

R⁷ is also chlorine or fluorine;

a compound having the formula ##STR6## wherein R⁸, R⁹ and R¹⁰ are each independently selected from hydrogen, branched or unbranched, substituted or unsubstituted alkyl having 1 to 18 carbon atoms, and alkylenecarbonyloxyalkyl having 3 to 18 carbon atoms;

a compound having the formula ##STR7## wherein R¹¹, R¹² and R¹³ are each independently selected from hydrogen and substituted or unsubstituted, branched or unbranched alkyl radicals containing from 1 to 10 carbon atoms;

a compound of the formula ##STR8## wherein R¹⁴ and R¹⁶ are each independently selected from substituted or unsubstituted alkyl containing from 1 to 18 carbon atoms, R¹⁵ is hydrogen, methyl, or substituted or unsubstituted aryl having 6 to 22 carbon atoms, and R¹⁶ is also substituted or unsubstituted alkoxy having 1 to 18 carbon atoms;

a compound having the formula ##STR9## wherein R¹⁷ and R¹⁸ are each independently selected from substituted or unsubstituted, branched or unbranched alkyl having 1 to 18 carbon atoms and R¹⁸ is hydrogen or methyl;

a compound having the formula ##STR10## wherein R²⁰ is hydrogen, substituted or unsubstituted branched or unbranched alkyl or alkoxy having 1 to 18 carbon atoms.

4. A copolyesterether composition according to claim 1 wherein said acid component comprises about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second acid selected from the group consisting of adipic acid, sebacic acid, glutaric and azelaic acid.

5. A copolyesterether composition according to claim 1 wherein said glycol component comprises about 70-95 mole % 1,4-cyclohexanedimethanol, about 5-30 mole % of a polyalkylene ether glycol and about 0-20 mole % of a third glycol selected from the group consisting of aliphatic glycols having 2 to 12 carbon atoms.

6. A copolyesterether composition according to claim 1 wherein said acid component comprises 1,4-cyclohexanedicarboxylic acid and a second acid selected from the group consisting of adipic acid, sebacic acid, glutaric acid, and azelaic acid, and said glycol component comprises 1,4-cyclohexanedimethanol, a polyalkylene ether glycol selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, and polytetramethylene ether glycol, and a third glycol selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol and 1,6-hexanediol, wherein said alkylene ether glycols have a molecular weight of about 600 to about 3000.

7. A copolyesterether composition according to claim 1 wherein 1,4-cyclohexanedicarboxylic acid has a trans isomer content of about 85 to 95%.

8. A copolyesterether composition according to claim 1 wherein said phenolic antioxidant is selected from the group consisting of tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H, 3H, 5H)-trione;

octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; and

1,6-hexamethylene-bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate, said ultraviolet light stabilizing compound is selected from the group consisting of 2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-ethoxy-2'"'"'-ethyloxanilide, and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and said hindered amine light stabilizing compound is selected from the group consisting of bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate, dimethylsuccinate polymer with 4-hyroxy-2,2,6,6-tetramethyl-1-piperidineethanol, and poly[(2,2,6,6-tetramethyl-4-piperidinyl)iminomethylene-2,2,6,6-tetramethyl-4-piperdinyl)imino[6-(octylamino)-1,3,5-triazine-4,2-diyl]].

20. A molded article of manufacture produced from the copolyesterether composition according to claim 1.

23. An extrusion blow molded article of manufacture produced from the copolyesterether according to claim 1.

26. A film of the copolyesterether composition according to claim 1.

9. A copolyesterether composition having a 264 psi heat deflection temperature greater than 60°

C. and an inherent viscosity of from about 0.8 to about 1.5, said copolyesterether comprising

A. a 100 mole % dicarboxylic acid component comprising about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second acid selected from the group consisting of aliphatic dicarboxylic acids having 3 to 12 carbon atoms.

B. a 100 mole % glycol component comprising about 70-95 mole % 1,4-cyclohexanedimethanol and about 5-30 mole % of a polyalkylene ether glycol having a molecular weight of about 600 to about 3000,

C. a stabilizing effective amount of the combination of

12. A copolyesterether composition according to claim 9 wherein said phenolic antioxidant is present in an amount of about 0.1 to about 0.5 weight %, said ultraviolet light stabilizing compound is present in an amount of about 0.5 to about 1.0 weight % and said hindered amine light stabilizing compound is present in an amount of about 0.25 to about 0.5 weight %, based on the weight of said copolyesterether.

13. A copolyesterether composition according to claim 9 wherein said acid component comprises about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second acid selected from the group consisting of adipic acid, sebacic acid, glutaric and azelaic acid.

14. A copolyesterether composition according to claim 9 wherein said glycol component comprises about 85-95 mole % 1,4-cyclohexanedimethanol, about 5-15 mole % of a polyalkylene ether glycol and about 0-10 mole % of a third glycol selected from the group consisting of aliphatic glycols having 2 to 12 carbon atoms.

15. A copolyesterether composition according to claim 12 wherein 1,4-cyclohexanedimethanol has a trans isomer content of at least 60%.

16. A copolyesterether composition according to claim 9 wherein said acid component comprises 1,4-cyclohexanedicarboxylic acid and a second acid selected from the group consisting of adipic acid, sebacic acid, glutaric acid, and azelaic acid, and said glycol component comprises 1,4-cyclohexanedimethanol, a polyalkylene ether glycol selected from the group consisting of polyethylene ether glycol, polypropylene ether glycol, and polytetramethylene ether glycol, and a third glycol selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol and 1,6-hexanediol, wherein said alkylene ether glycols have a molecular weight of about 800 to about 1200.

17. A copolyesterether composition according to claim 9 wherein 1,4-cyclohexanedicarboxylic acid has a trans isomer content of about 85 to 95%.

18. A copolyesterether composition according to claim 9 wherein said phenolic antioxidant is selected from the group consisting of pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H, 3H, 5H)-trione;

octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate; and

1,6-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate, said ultraviolet light stabilizing compound is selected from the group consisting of 2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-ethoxy-2'"'"'-ethyloxanilide, and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and said hindered amine light stabilizing compound is selected from the group consisting of bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate, dimethylsuccinate polymer with 4-hyroxy-2,2,6,6-tetramethyl-1-piperdineethanol, and poly[(2,2,6,6-tetramethyl-4-piperidinyl)iminomethylene-2,2,6,6-tetramethyl-4-piperdinyl)imino[6-(octylamino)-1,3,5-triazine-4,2-diyl]].

21. A molded article of manufacture produced from the copolyesterether composition according to claim 9.

22. A molded article of manufacture produced from the copolyesterether composition according to claim 16.

24. An extrusion blow molded article of manufacture produced from the copolyesterether according to claim 9.

25. An extrusion blow molded article of manufacture produced from the copolyesterether according to claim 16.

27. A film of the copolyesterether composition according to claim 9.

28. A film of the copolyesterether composition according to claim 16.

10. at least one hindered phenolic antioxidant,at least one ultraviolet light stabilizing compound selected from the group consisting of a compound having the formula ##STR11## wherein R⁵, R⁶, and R⁷ are each independently selected from hydrogen, hydroxyl, branched or unbranched, substituted or unsubstituted alkyl or alkoxy radicals containing from 1 to 18 carbon atoms, aryl, and alkylenearyl containing from 7 to 22 carbon atoms;

R⁷ is also chlorine or fluorine;

a compound having the formula ##STR12## wherein R⁸, R⁹ and R¹⁰ are each independently selected from hydrogen, branched or unbranched, substituted or unsubstituted alkyl having 1 to 18 carbon atoms, and alkylenecarbonyloxyalkyl having 3 to 18 carbon atoms;

a compound having the formula ##STR13## wherein R¹¹, R¹² and R¹³ are each independently selected from hydrogen and substituted or unsubstituted, branched or unbranched alkyl radicals containing from 1 to 10 carbon atoms;

a compound of the formula ##STR14## wherein R¹⁴ and R¹⁶ are each independently selected from substituted or unsubstituted alkyl containing from 1 to 18 carbon atoms, R¹⁵ is hydrogen, methyl, or substituted or unsubstituted aryl having 6 to 22 carbon atoms, and R¹⁶ is also substituted or unsubstituted alkoxy having 1 to 18 carbon atoms;

a compound having the formula ##STR15## wherein R¹⁷ and R¹⁸ are each independently selected from substituted or unsubstituted, branched or unbranched alkyl having 1 to 18 carbon atoms and R¹⁹ is hydrogen or methyl;

a compound having the formula ##STR16## wherein R²⁰ is hydrogen, substituted or unsubstituted branched or unbranched alkyl or alkoxy having 1 to 18 carbon atoms,

11. at least one hindered amine light stabilizing compound having the formulae ##STR17## wherein m and n are each integers of from 1 to 20, R¹, R², R³ and R⁴ are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 22 carbon atoms, alkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 12 carbon atoms, hydroxyalkyl having 1 to 18 carbon atoms, and esters of said hydroxyalkyl;

and alkylenecarboxylic acid having 2 to 18 carbon atoms and esters, amides and metal salts of said alkylenecarboxylic acid.

19. A copolyesterether composition having a 264 psi heat deflection temperature greater than 60°

C. and an inherent viscosity of about 0.8 to about 1.5, said copolyesterether comprising

A. a 100 mole % dicarboxylic acid component comprising about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second acid selected from the group consisting of aliphatic dicarboxylic acids having 3 to 12 carbon atoms,

B. a 100 mole % glycol component comprising about 85-95 mole % 1,4-cyclohexanedimethanol having a trans isomer content of at least 60% and about 5-15 mole % of a polyalkylene ether glycol having a molecular weight of about 800 to about 1200,

C. the combination of about 0.1 to about 0.5 weight % pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), about 0.5 to about 1.0 weight % 2-ethoxy-2'"'"'-ethyloxanilide, and about 0.25 to about 0.5 weight % of a polyester of succinic acid and N-β

-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine.

29. The method for stabilizing a copolyesterether composition having a 264 psi heat deflection temperature greater than 60°

C. and an inherent viscosity of about 0.8 to about 1.5, said copolyesterether comprising a 100 mole % dicarboxylic acid component comprising about 80-100 mole % 1,4-cyclohexanedicarboxylic acid having a trans isomer content of at least 70% and about 0-20 mole % of a second acid selected from the group consisting of aliphatic dicarboxylic acids having 3-12 carbon atoms, a 100 mole % glycol component comprising about 70-95 mole % 1,4-cyclohexanedimethanol, and about 5-30 mole % of a polyalkylene ether glycol having a molecular weight of about 600 to about 3000, said method comprising the step of incorporating into said copolyesterether composition a stabilizing effective amount of the combination of

1. at least one hindered phenolic antioxidant,

2. at least one ultraviolet light stabilizing compound compatible with said copolyesterether, and

3. at least one hindered amine light stabilizing compound having the formulae ##STR18## wherein m and n are each integers of from 1 to 20, R¹, R², R³ and R⁴ are each independently selected from hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, aryl having 6 to 22 carbon atoms, alkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 12 carbon atoms, hydroxyalkyl having 1 to 18 carbon atoms, and esters of said hydroxyalkyl; and

alkylenecarboxylic acid having 2 to 18 carbon atoms and esters, amides and metal salts of said alkylenecarboxylic acid.