Performance and synergistic effect of phenolic and thio antioxidants in ABS graft copolymers

Abstract

The synergistic effect of phenolic and thio antioxidants on the stabilization of acrylonitrile-butadiene-styrene (ABS) graft copolymers has been studied. Three commercial antioxidants Irganox245, Irganox1076 and dilauryl thiodipropionate (DLTP) were selected. Formulations based on hindered phenols and secondary antioxidant DLTP were prepared. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties and yellowness index. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were also used to assess the stability. The results indicated that the combination of Irganox245 and DLTP showed much better stabilization effect than the individual components due to the strong synergistic effect. Only weak synergism could be observed in the formulation that contained Irganox1076 and DLTP. Irganox1076 and Irgnox1076/DLTP exhibited similar behaviors between antioxidants with the highest and lowest efficiencies.

Key words： antioxidant; ABS graft copolymers; synergistic effect

Acknowledgments

The financial supports of the Jilin Provincial Science and Technology Department (200505252) were gratefully acknowledged.

References

1 Tiganis B E, Burn L S, Davis P, Hill A J. Thermal degradation of acrylonitrile-butadiene-styrene (ABS) blends. Polym Degrad Stab, 2002, 76 (3): 425–434

2 Boldizar A, Möller K. Degradation of ABS during repeated processing and accelerated aging. Polym Degrad Stab, 2003, 81 (2): 359–336

3 Scott G, Tahan M. Comparison of the photo-oxidative behaviour of some polybutadiene-based polyblends. European Polym J, 1977, 13(12): 981–987

4 Shimada J. The mechanism of oxidative degradation of ABS resin. Part 1. The mechanism of thermooxidative degradation. J Appl Polym Sci, 1968, 12(4): 655–669

5 Suzuki M, Charles A W. The thermal degradation of acrylonitrile-butadiene-styrene terpolymer as studied by TGA/FTIR. Polym Degrad Stab, 1995, 47(2): 217–221

6 Adediyi J B. Clarification and discussion of chemical transformations involved in thermal and photo-oxidative degradation of ABS. European Polym J, 1984, 20(3): 291–299

7 Vulic I, Vitarelli G, Zenner J M. Structure-property relationships: phenolic antioxidants with high efficiency and low colour contribution. Polym Degrad Stab, 2002, 78(1): 27–34

8 Peña J M, Allen N S, Edge M, Liauw C M, Valange B. Studies of synergism between carbon black and stabilizers in LDPE photodegradation. Polym Degrad Stab, 2001, 72(2): 259–270

9 Allen N S, Barcelona A, Edge M, Wilkinson A, Merchan C G. Aspects of the thermal and photostabilisation of high styrene-butadiene copolymer (SBC). Polym Degrad Stab, 2006, 91(6): 1395–1416

10 Shanks D, Al-Maharik N, Malmström J, Engman L, Eriksson P, Stenberg B, Reitberger T. Improved antioxidant formulations for polymeric materials-synergistic protective effects in combinations of organotellurium compounds with conventional phenolic antioxidants or thiols. Polym Degrad Stab, 2003, 81(2): 261–271

11 Alariqi S A S, Kumar A P, Rao B S M, Singh R P. Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers. Part II. Polypropylene matrix. Polym Degrad Stab, 2007, 92(2): 299–309

12 Kolawole E G. Thermal and photooxidation of polyolefins in the presence of 3,5-ditertiarybutyl-4-hydroxybenzyl thioglycollate, zinc diethyldithio carbamate, and irganox 1076. J Appl Polym Sci, 1982, 27(9): 3437–3448

13 Shanina E L, Konradov A A, Zaikov G E. Synergy effects in binary and ternary mixtures of inhibitors in polypropylene autooxidation. Polym Degrad Stab, 1999, 63(2): 177–181

14 Jonge C, Maeden F, Biemond M, Huysmans W, Mijs W J. Antioxidative properties of phenyl-substituted phenols. III. Model studies of synergistic actions between primary and secondary antioxidants. J Polymer SCI, 1976, 57(1): 197–204

15 Billmeyer F W, Sultzman, eds. Principles of Colour Technol. New York: Interscience, 1966, 38

16 Rosík L, Kovářová J, Pospíšil J. Lifetime prediction of ABS polymers based on thermoanalytical data. Journal of Thermal Analysis and Calorimetry, 1996, 46(2): 465–470

17 Bauer I, Habicher W D, Rautenberg C, Al-Malaika S. Antioxidant interaction between organic phosphites and hindered amine light stabilisers during processing and thermoxidation of polypropylene. Polym Degrad Stab, 1995, 48(3): 427–440

18 Blom H, Yeh R, Wojnarowski R, Ling M. Detection of degradation of ABS materials by DSC. Journal of Thermal Analysis and Calorimetry, 2006, 83(1): 113–115

19 Földes E, Lohmeijer J. Polymer/additive compatibility: study of primary antioxidants in PBD. J Appl Polym Sci, 1997, 65(4): 761–775

20 Zweifel H, editor. Stabilization of Polymeric Materials. Berlin: Springer-Verlag, 1998

21 Al-Malaika S, Goodwin C, Issenhuth S, Burdick D. The antioxidant role of α-tocopherol in polymers II. Melt stabilising effect in polypropylene. Polym Degrad Stab, 1999, 64(1): 145–156

22 Alariqi S A S, Kumar AP, Rao B S M, Tevtia A K, Singh R P. Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers. Polym Degrad Stab, 2006, 91(10): 2451–2464

23 Roger C L, Norman B C, Kenneth G T, eds. Polymer durability degradation, stabilization, and lifetime prediction. Roger C L, Norman B C, Kenneth G T, eds. Advances in Chemistry Series. Washington DC: American Chemical Society, 1996, 359–374

24 Földes E, Lohmeijer J. Relationship between chemical structure and performance of primary antioxidants in PBD. Polym Degrad Stab, 1999, 66(1): 31–39

25 Scott G. Atmospheric Oxidation and Antioxidants. Elsevier: 1965

26 Yachigo S, Sasaki M, Kojim F. Studies on polymer stabilizers. Part II. A new concept of a synergistic mechanism between phenolic and thiopropionate type antio xidants. Polym Degrad Stab, 1992, 35(2): 105–113