摘要
橡胶的老化与防老化是橡胶理论和应用的一个重要问题。当前橡胶防老剂的发展方向是高效、多功能化、环保和低成本。合成新型环保型高效多功能橡胶防老剂对于橡胶制品的使用和橡胶工业的发展具有重要的理论和实际意义。
本文合成了14种新型2-巯基苯并咪唑稀土配合物,通过红外光谱分析、元素分析、X射线衍射等方法对配合物进行了表征,确定配合物的结构式为:REL2(OH)?XH2O(RE=镧~镥,除钷外,L=2-巯基苯并咪唑,X=1或2)。同时选择天然橡胶和丁苯橡胶两种橡胶体系,研究了2-巯基苯并咪唑稀土配合物对天然橡胶硫化胶和丁苯橡胶硫化胶的热氧老化、紫外光老化、臭氧老化及动态老化性能的影响及其作用机理,并与防老剂4010NA及防老剂MB进行了比较。
选用自制的十四种稀土配合物,与天然橡胶按常规方法进行混炼、硫化制得硫化胶。采用红外光谱、X射线光电子能谱、交联密度测定、力学性能测试等方法研究了钐配合物对天然橡胶硫化胶热氧老化过程的化学组成、硫化胶结构和力学性能的影响。通过热分析方法探讨了钐配合物对天然橡胶硫化胶防老化作用的机理。结果表明钐配合物对天然橡胶硫化胶有显著的防老化作用,其防老化效果优于防老剂4010NA和防老剂MB。钐配合物一方面通过结构中的硫醚键分解氢过氧化物,另一方面稀土钐离子与老化过程中产生的含氧自由基及含氧化合物作用,从而达到了较好的防老化效果。热氧化动力学计算得出添加钐配合物天然橡胶硫化胶的热氧化活化能高于添加防老剂4010NA和添加防老剂MB硫化胶的热氧化活化能值。
通过全反射红外光谱、力学性能测试、表面形貌分析等方法研究了2-巯基苯并咪唑钐配合物对天然橡胶耐紫外光老化、臭氧老化和疲劳老化性能的影响,并与橡胶防老剂4010NA及防老剂2-巯基苯并咪唑进行了比较。结果表明稀土配合物的加入可以对天然橡胶硫化胶紫外光老化、臭氧老化和疲劳老化起到较好的防护作用,其综合防老化效果优于防老剂4010NA和防老剂MB,但防臭氧老化效果稍逊于防老剂4010NA。
采用自制的十四种稀土配合物,与丁苯橡胶按常规方法进行混炼、硫化制得硫化胶,热氧老化性能测试表明2-巯基苯并咪唑稀土配合物对丁苯橡胶硫化胶的热氧老化有较好的防老化效果。分别采用微分法和积分法计算出了添加不同防老剂丁苯橡胶硫化胶的热氧化活化能,两种方法计算结果相近。利用Ozawa公式计算出了不同失重百分率时的热氧化活化能,结果显示,添加钐配合物丁苯橡胶硫化胶在不同失重率对应的活化能比添加防老剂4010NA及添加防老剂MB硫化胶相应的活化能数值都高,说明2-巯基苯并咪唑钐配合物对丁苯橡胶硫化胶的热氧老化防护效果较防老剂4010NA及防老剂MB更为显著。
通过全反射红外光谱、力学性能测试、表面形貌分析等方法,研究了合成的2-巯基苯并咪唑稀土钐配合物对丁苯橡胶紫外光老化、臭氧老化和疲劳老化性能的影响,并与橡胶防老剂4010NA及防老剂2-巯基苯并咪唑进行了比较。研究表明稀土配合物的加入可以对丁苯橡胶硫化胶紫外光老化、臭氧老化和疲劳老化起到较好的防护作用,其综合防老化效果优于防老剂4010NA和防老剂MB,但防臭氧老化效果稍逊于防老剂4010NA。
Ageing and anti-ageing of rubber is one of the most important problems in theoretical research and applied sciences of rubber. The current direction of development of rubber anti-ageing agent are high performance, multi-functional, environmental friendly and low-cost. Synthesis of new types of multi-functional rubber anti-ageing agent will play an important theoretical and practical part in rubber products and the development of rubber industry.
Fourteen rare earth complexes with 2-Mercaptobenzimidazole were synthesized and characterized by IR spectra, elemental analyses, X-ray diffraction and thermal analyses. The results indicated that the composition of the complexes is REL2(OH)?XH2O (RE = La～Lu, except for Pm, L = 2-mercaptobenzimidazole, x =1 or 2). Natural rubber(NR) vulcanizates and styrene-butadiene rubber(SBR) vulcanizates were prepared with the rare earth complexes. The antioxidative properties and mechanisms of the rare earth complexes in the NR vulcanizates and SBR vulcanizates were analyzed and compared with antioxidant 4010NA and antioxidant MB.
The NR vulcanizates with fourteen kinds of rare earth complexes were prepared according to the conventional processes. The antioxidative properties and mechanisms of the Sm(III) complex in the NR vulcanizates were analyzed by attenuated total-reflectance Fourier transform infrared (FTIR-ATR) spectroscopy, X-ray photoelectron spectroscopy (XPS), crosslinking density determination, mechanical testing and thermogravimetric analysis (TGA). It was found that the Sm(III) complex showed the significant antioxidative effect in the NR vulcanizates through two functions: the thioether bond which can decompose the peroxide and the Sm(III) ion which can capture and inactivate the oxy radicals. The apparent thermo-oxidation activation energy (E) of the NR vulcanizates were calculated by the Kissinger and Flynn-Wall-Ozawa methods, respectively. The results showed that the NR vulcanizate with the Sm(III) complex had higher thermo-oxidation activation energy than the samples with antioxidant 4010NA and antioxidant MB.
The effect of the Sm(III) complex on the photo-ageing, ozone ageing and fatigue ageing of NR vulcanizates were investigated by attenuated total-reflectance Fourier transform infrared (FTIR-ATR) spectroscopy and optical microscopy. The anti-ageing stability of the NR vulcanizates were found to be improved markedly by the addition of Sm(III) complex. The comprehensive antioxidant effect of the Sm(III) complex was superior to that of antioxidant 4010NA and antioxidant MB, but the ozone-resisting performance of the Sm(III) complex was slightly lower than that of antioxidant 4010NA.
The SBR vulcanizates with fourteen kinds of rare earth complexes were prepared according to the conventional processes. The antioxidative properties and mechanisms of the Sm(III) complex in the SBR vulcanizates were analyzed. It was found that the Sm(III) complex showed the significant antioxidative effect in the SBR vulcanizates. The apparent thermo-oxidation activation energy (E) of the SBR vulcanizates were calculated by the Kissinger and Flynn-Wall-Ozawa methods, respectively. The results showed that the SBR vulcanizate with the Sm(III) complex had higher thermo-oxidation activation energy than the samples with antioxidant 4010NA and antioxidant MB.
The effect of the Sm(III) complex on the photo-ageing, ozone ageing and fatigue ageing of SBR vulcanizates were investigated by attenuated total-reflectance Fourier transform infrared (FTIR-ATR) spectroscopy and optical microscopy. The anti-ageing stability of the SBR vulcanizates were found to be improved markedly by the addition of Sm(III) complex. The comprehensive antioxidant effect of the Sm(III) complex was superior to that of antioxidant 4010NA and antioxidant MB, but the ozone-resisting performance of the Sm(III) complex was slightly lower than that of antioxidant 4010NA.
引文
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