( 自然科学版 ) 40 10 Journal of South China University of Technology Vol 40 No 10 2012 10 Natural Science Edition October 2012 1000-565X 2012 10-0128-06 C- / * 1 1 1 1 2 2 1 510640 2 528521 以镧和维生素 C 为原料制备了一种新型稀土配合物, 将该新型稀土配合物作为 一种新型防老剂应用于天然橡胶 / 炭黑 ( NR /CB) 复合材料中, 研究了该稀土配合物对 NR /CB 混炼胶硫化特性和硫化胶力学性能的影响, 通过红外光谱 力学性能保持率及表 面形貌变化详细分析了该稀土配合物对 NR /CB 硫化胶耐老化性能的影响, 并与常用橡胶 防老剂 4010NA RD 和 MB 进行了比较 结果表明 : 维生素 C- 稀土配合物对 NR /CB 混炼 胶具有一定的硫化促进作用, 并能提高 NR /CB 硫化胶的力学性能 ; 维生素 C- 稀土配合物 在 NR /CB 复合材料中有优良的抗老化作用, 其抗热氧老化和抗紫外光老化效果与 4010NA RD 相近, 优于 MB, 其抗臭氧老化性能尤为突出, 显著优于 RD MB 和具有突出 抗臭氧性能的 4010NA 维生素 C; 稀土配合物 ; 天然橡胶 ; 炭黑 ; 复合材料 ; 热氧老化 ; 紫外光老化 ; 臭氧老化 TQ33 doi: 10 3969 /j issn 1000-565X 2012 10 018 O S N 2-5 6-8 9 2-6-8 1 C C / NR /CB 2012-07-10 * 863 2010AA03A406 51003031 973 2010CB635109 1954- E-mail psyfluo@ scut edu cn 1980- E-mail zxjia@ scut edu cn
10 C- / 129 1 实验 1 1 1 GT-0500 GB / N330 T7762 2003 40 CZ DM 4010NA RD MB C Olympus-BX51 C 500 C 20 ~ 30 0 5 ~ 1 0 h 2 结果与讨论 C 2 1 30 ~ 60 La C 6 H 7 O 6 3 3H 2 O 5 NR /CB La C C 6 H 7 O 6 O 1 1 1 1 C 1 2 100 40 5 2 CZ 1 5 DM 0 5 1 5 2 160 3 CZ DM 25 t 143 1 3 UR 1 NR /CB 2030 GB /T 9869 1997 Fig 1 Curing curves of NR / CB compounds with different T 90 antioxidants UT 1 1 NR /CB 2080 GB /T528 1998 Table 1 Curing parameters of NR / CB compounds with different 500 mm /min antioxidants Nicolet Migna 760 NR /CB C FTIR-ATR GT-7017 GB /T 3512 2001 100 GT-QUV /SPRAY GB /T 16585 1996 50 340 nm 0 83 107 mg /m 3 20% T 90 CRI T 10 /min T 90 /min M L / dn m M H / dn m CRI /min -1 3 22 8 11 0 85 26 87 20 33 2 13 6 05 1 01 27 03 25 26 MB 2 35 8 14 0 91 24 85 17 46 RD 3 18 7 51 0 99 27 14 21 36 2 59 7 10 1 17 28 82 23 06 4010NA 1 M L M H CRI
130 ( 自然科学版 ) 40 C 2 NR /CB 4f Table 2 Mechanical properties of NR / CB vulcanizates with different antioxidants 300% A /MPa /MPa /% / kn m C 6 27 T 10 1 C 1 4010NA 7 14 MB MB 6 88 28 93 29 89 27 74 447 466 488 56 35 61 18 58 34 56 59 58 RD 2 2 RD 7 02 30 19 470 62 57 58 4010NA 7 56 30 65 459 63 35 61 2 3 9 NR /CB FTIR-ATR 2 2 C 1710 ~ 1750 cm - 1 NR /CB 300% 3000 ~ 3 600 cm - 1 C 10 NR /CB 72 96 120 h FTIR-ATR 2 Fig 2 2 NR /CB FTIR-ATR spectra of NR / CB vulcanizates with different antioxidants after different time in thermo-oxidative ageing FTIR-ATR CH 2 α 3 3 NR/CB RD 4010NA NR /CB 100 1 700 ~ 1750 cm - 1 A C O /A CH2 C MB C A CH2 RD 4010NA MB
10 C- / 131 3 Fig 3 2 4 C NR /CB NR /CB 100 3 3 C MB RD 4010NA C NR /CB RD 4010NA 100 MB C Variations of absorbance peak areas of carbonyl group of NR / CB vulcanizates with different antioxidants in RD 4010NA MB thermo-oxidative ageing process at 100 FT-IR 3 NR /CB 100 Table 3 Mechanical properties retention of NR / CB vulcanizates with different antioxidants after thermo-oxidative ageing at 100 72 h 96 h 120 h /% /% /% /% /% /% 60 5 54 6 48 5 47 7 43 2 43 6 C 70 2 60 7 61 6 53 4 53 5 47 9 MB 64 9 75 7 48 9 65 4 44 9 64 3 RD 77 3 62 9 67 8 54 6 64 6 50 7 4010NA 69 5 57 3 63 6 53 60 9 50 6 2 5 C NR /CB MB C RD NR /CB 4010NA 144 h 48 96 144 h C RD 4010NA 4 NR/CB 4 MB 144h NR /CB C NR /CB RD 4010NA Table 4 4 NR /CB Mechanical properties retention of NR / CB vulcanizates with different antioxidants after ultraviolet aging 48 h 96 h 144 h /% /% /% /% /% /% 100 0 95 5 93 8 82 8 85 6 69 0 C 100 0 98 3 96 5 86 5 91 1 81 8 MB 101 0 100 0 95 1 85 9 89 0 83 6 RD 99 4 92 2 98 1 84 4 90 1 78 7 4010NA 97 1 90 6 95 7 80 9 90 6 77 3 4 2 6 C NR /CB C RD 4010NA MB
132 ( 自然科学版 ) 40 NR /CB 4 4 a 48 h C NR /CB 4010NA MB RD NR /CB 0 4 b 4 a C NR /CB RD MB 4010NA 5 Fig 5 NR /CB 48 h Surface morphology of NR / CB vulcanizates with different antioxidants after ozone ageing for 48 h C C 7-8 C 3 结论 1 C NR /CB T 90 T 10 4 NR /CB 2 C NR /CB MB Fig 4 Mechanical properties retention of NR / CB vulcanizates with different antioxidants after ozone ageing RD 4010NA C 48 h 500 5 5 3 C NR /CB 48 h C MB RD 4010NA 4010NA 4 C NR /CB MB RD 4010NA C 1 J 4010NA 2009 50 5 56-67
10 C- / 133 Li Ang Aging phenomenon and aging mechanism of rubber J Special Purpose Rubber Products 2009 50 5 56-67 2 Yang Shu-yan Liu Lan Jia Zhi-xin et al Structure and mechanical properties of rare-earth complex La-GDTC modified silica/sbr composites J Polymer 2011 52 12 2701-2710 3 O O'- aging behavior of natural rubber vulcanizates J International Journal of Polymeric Materials 2010 59 9 663-679 J 2007 28 4 59-62 Lin Xin-hua Chen Zhao-hui Wang Di-zhen Effects of praseodymium O O'-dioctyldithiophosphate on properties of natural rubber J Chinese Rare Earths 2007 28 4 59-62 4 in natural rubber vulcanizates J Acta Polymerica Sinica J 2004 22 2011 3 320-326 3 299-306 Zhang Wei-guang Yin Xia Fan Jun et alprogress in synthesis and application of complexes of rare earth with organic ligands containing sulphur atoms J Journal of The Chinese Rare Earth Society 2004 22 3 299-306 5 thermal and natural ageing of ethylene-propylene-diene J 2005 7 3-6 monomer monomer EPDM rubber used in automotive Huang Miao-you Fan Yi Zhang Wei-guang Research on properties of novel rare earth accelerant in coordinated reaction of natural rubber J World Rubber Industry 2005 7 3-6 6 Xie Chan Jia Zhi-xin Luo Yuan-fang et al Thermal-oxidative aging properties of natural rubber vulcanizates with Sm Ⅲ complex as antioxidant J China Synthetic Rubber Industry 2010 33 2 158 7 Xie Chan Jia Zhi-xin Jia De-min et al Effect of Dy III complex with 2-mercaptobenzimidazole on thermo-oxidation 8 2- J 2011 3 320-326 Xie Chan Jia Zhi-xin Luo Yuan-fang et al Antioxidant effect of Sm Ⅲ complex with 2-mercaptobenzimidazole 9 Lin Y L Zhang A Q Wang L S Rare earth compounds modified carbon black filled powdered natural rubber preparation morphology and properties J Journal of Applied Polymer Science 2008 108 3 1393-1401 10 Delor-Jestin F Lacoste J Barrois-Oudin N et al Photo- applications influence of carbon black crosslinking and stabilizing agents J Polymer Degradation and Stability 2000 67 3 469-477 Antiaging Effect of Vitamin C-Rare Earth Complex on Natural Rubber / Carbon Black Composites Luo Yuan-fang 1 Yang Chao 1 Jia Zhi-xin 1 Jia De-min 1 Chen Jun 2 Zheng De 2 1 School of Materials Science and Engineering South China University of Technology Guangzhou 510640 Guangdong China 2 Guangdong Winner Functional Materials Co Ltd Foshan 528521 Guangdong China Abstract A novel rare earth complex was prepared from lanthanum La and vitamin C and was used as a new type of antioxidant in natural rubber /carbon black NR /CB composites Then the effects of the vitamin C-rare earth complex on the curing characteristics of NR /CB compounds and the mechanical properties of NR /CB vulcanizates were investigated Moreover by means of FT-IR and according to the retention of mechanical properties and the variation of surface morphology the effects of the rare earth complex on the antiaging properties of the NR /CB vulcanizates were also analyzed in detail and were compared with those of the commonly-used rubber antioxidants 4010NA RD and MB The results show that 1 the rare earth complex can accelerate the vulcanization of the NR / CB compounds to a certain degree and improve the mechanical properties of the NR /CB vulcanizates 2 the rare earth complex has a good antiaging effect on the NR /CB vulcanizates 3 the thermo-oxidative aging resistance and UV aging resistance of the rare earth complex are close to those of 4010NA and RD and are superior to those of MB and 4 the ozone aging resistance of the rare earth complex is particularly strong for the NR /CB vulcanizates which is superior to those of RD and MB as well as to those of 4010NA with an excellent ozone aging resistance Key words vitamin C rare earth complex natural rubber carbon black composites thermo-oxidative aging ultraviolet aging ozone aging 孙涛