Thermal oxidative degradation of styrene-butadiene rubber (SBR) studied by 2D correlation analysis and kinetic analysis

被引:49
作者
Guo, Lili [1 ]
Huang, Guangsu [1 ]
Zheng, Jing [1 ]
Li, Guangxian [1 ]
机构
[1] Sichuan Univ, Coll Polymer Sci & Engn, State Key Lab Polymer Mat Engn, Chengdu 610065, Peoples R China
基金
美国国家科学基金会;
关键词
Thermal kinetics; 2D-FTIR; SBR; Curve fitting; Degradation mechanism; DECOMPOSITION; POLYSTYRENE; POLYBUTADIENE; COPOLYMERS; PARAMETERS; RAMAN; FTIR;
D O I
10.1007/s10973-013-3348-0
中图分类号
O414.1 [热力学];
学科分类号
摘要
The thermal oxidation degradation of styrene-butadiene rubber (SBR) was investigated by in situ FTIR, 2D-FTIR, and programming heating DSC. The results of analyses suggest that the degradation reaction is an autocatalytic process and mainly occurs on the aliphatic part instead of benzene pendants. Based on the results of in situ FTIR and 2D-FTIR, the oxidation process can be divided into three stages. In stage one, just two carbonyl peaks appear, namely 1,697 cm(-1) (conjugate carbonyls) and 1,727 cm(-1) (saturated carbonyls), and the generation speed is 1,697 > 1,727 cm(-1). Yet the peaks appearing at 1,777 cm(-1) belonged to peresters and anhydrides generating in stages two and three. The generation sequences are: 1,698 > 1,727 > 1,777 cm(-1) for stage two; and 1,698 < 1,727 < 1,777 cm(-1) for stage three. According to DSC results, the thermal oxidation of SBR contains four steps. The first step is the generation of alkyl radicals and the accumulation of hydroperoxide species. The second step is initial oxidation stage mainly producing conjugate carbonyls. The third step is deep oxidation process generating diverse carbonyls. The fourth is chain termination reaction, in which step the generation rates of anhydrides and peresters are the fastest due to bi-radical termination of alkoxy radicals and the consumption of conjugate carbonyl. Furthermore, crosslinking reactions occur during the whole thermal oxidation.
引用
收藏
页码:647 / 657
页数:11
相关论文
共 29 条
[1]  
Allen NS, 2001, POLYM DEGRAD STABIL, V71, P113
[2]   Thermal and photooxidation of high styrene-butadiene copolymer (SBC) [J].
Allen, NS ;
Barcelona, A ;
Edge, M ;
Wilkinson, A ;
Merchan, CG ;
Quiteria, VRS .
POLYMER DEGRADATION AND STABILITY, 2004, 86 (01) :11-23
[3]  
[Anonymous], 2DSHIGE C SHIG MOR
[4]   TG-DSC-FTIR-MS study of gaseous compounds evolved during thermal decomposition of styrene-butadiene rubber [J].
Arockiasamy, Antonyraj ;
Toghiani, Hossein ;
Oglesby, David ;
Horstemeyer, M. F. ;
Bouvard, J. L. ;
King, Roger L. .
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 2013, 111 (01) :535-542
[5]   Influence of montmorillonite nano-dispersion on polystyrene photo-oxidation [J].
Bottino, F. A. ;
Di Pasquale, G. ;
Fabbri, E. ;
Orestano, A. ;
Pollicino, A. .
POLYMER DEGRADATION AND STABILITY, 2009, 94 (03) :369-374
[6]   Photoreaction and molecular reorientation in a nanoscaled film of poly(methyl 4-(methacryloyloxy)cinnamate) studied by two-dimensional FTIR and UV correlation spectroscopy [J].
Chae, B ;
Lee, SW ;
Ree, M ;
Jung, YM ;
Kim, SB .
LANGMUIR, 2003, 19 (03) :687-695
[7]   Generalized correlation NMR spectroscopy [J].
Eads, CD ;
Noda, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (06) :1111-1118
[8]   NEW METHODS FOR EVALUATING KINETIC PARAMETERS FROM THERMAL ANALYSIS DATA [J].
FRIEDMAN, HL .
JOURNAL OF POLYMER SCIENCE PART B-POLYMER LETTERS, 1969, 7 (1PB) :41-&
[9]   Two-dimensional fluorescence correlation spectroscopy with modulated excitation [J].
He, Y ;
Wang, GF ;
Cox, J ;
Geng, L .
ANALYTICAL CHEMISTRY, 2001, 73 (10) :2302-2309
[10]   Thermal properties of cis-1,4-poly(butadiene) [J].
Janowska, G ;
Slusarski, L .
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 2001, 65 (01) :205-212