【作者】 张士齐； 贾红兵； 吉庆敏； 金志刚； 文威； 黄爱华； 周翠微；

【Author】 S.Q.Zhang H.B.Jia Q.G.Ji Z.G.Jin W.Wen (Dept.of Polymer Science,Nanjing Univ.of Sci.& Technol.Nanjing,210094) A.H.Huang (Nanjing Institute of Power,Nanjing,210094) C.W.Zhou (Nanjing University,Nanjing,210094)

【机构】 南京理工大学高分子系； 南京动力高等专科学校； 南京大学；

【摘要】 <正>橡胶制品在机械力的作用下,橡胶大分子断裂形成自由基,它们经歧化、转移、再化合等多种途径终止,对制品使用寿命影响很大。研究硫化胶大分子在疲劳作用下链自由基形成、转化、终止的特性,有较大价值。但是,一般情况下,链自由基的终止反应活化能很低,速度根快,在常温下很不稳定,研究多在液氮温度下进行,这与橡胶制品通常在室温大气中使用的条件相去甚远。本文用电子自旋共振及灰色系统理论研究了硫化胶在室温大气条件下疲劳形成的自由基的稳定性。硫化橡胶交联网络在室温大气中疲劳断裂形成的大分子链氧自由基 RO·很稳定,在室温下停放37个月后仍有强烈的电子自旋共振信号。在液氮温度和常温下停放,硫化胶大分子链氧自由基 RO·的衰减行为都遵循指数方程表达的能量变化规律。其数学模型表示为：液氮温度,密闭体系 x₁^（1）（k+1）=478e^3.62k-378 室温,密闭体系 x₂^（1）（k+1）=341e^2.83k-270 室温,开放体系 x₃^（1）（k+1）=182e^4k-143更多还原

【Abstract】 Rubber products,while in use,are often under the influence of mechanical forces.This brings about fractures of macromolecules and formation of macroradicals[1-6].These radicals may terminate by dispropotionation,transformation and coupling with others,which has very important influence on the life of robber products.It is very necessary to study the properties of formation,transformation and termination of these macroradicals.However,radicals terminate very quickly at room tempersture and related research has been done at liquid nitrogen temperature.This is not suitable for rubber system which is often used at room temperature In this paper,ESR and grey system theory[7]are used to study the stability of macroradical formed during vulcanizes fatigue. These macroradicals are very stable.When the rumples were stored for 37 months at room temperature,ESR signals of macroradicals are still strong Kinetics of the macroradical decay at liquid nitrogen and room temperature follow exponential equation energy change law The mathematics models of macroradical RO·at different environment follow as: liquid nitrogen temperature.,closed system x₁¹（k+1）=478e^3.62k-378 room temperature,closed system x₂¹（k+1）=341e^2.83k-270 room temperature,open system x₃¹（k+1）=182e^4k-143更多还原