广角X射线衍射原位研究丁烯/乙烯共聚物循环拉伸诱导相转变
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摘要
利用力学拉伸和广角X射线衍射联用方法,原位研究了含有1.5%(摩尔分数)共聚单元的丁烯/乙烯无规共聚物在循环拉伸过程中FormⅡ晶型向FormⅠ晶型相转变过程.通过力学性质和相转变动力学关联,发现第一次拉伸过程中相转变开始于屈服区域;在循环拉伸过程中,相转变在回复及二次拉伸屈服前都可进行,但大于第一次屈服强度的拉伸应力可以显著加速相转变动力学.同时,还在该丁烯/乙烯共聚物体系中发现转变相FormⅠ含量与拉伸应力的对应性.研究成果有助于认识丁烯/乙烯共聚物的宏观性质与微观晶体结构关系,为晶体结构调控和新型共聚物开发提供基础和指导.
The cyclic-stretching induced phase transition of a butene/ethylene copolymer containing 1.5%(mole fraction) co-units was explored with mechanical testing and wide angle X-ray diffraction,and the mechanical performance was correlated with phase transition kinetics.The results show that during the initial stretching,the phase transition was triggered with yielding.On the other hand,during the recovery and secondary stretching,the phase transition was independent of yielding.However,the phase transition kinetics can be significantly accelerated when the stretching strength exceeds the stress of the initial yielding.Moreover,the correspondence between the mechanical properties and the FormⅠ fraction indicates a stress-dominant mechanism for the phase transition.The results shed light on the relationship between macroscopic mechanical properties and microscopic crystalline structures and provide the foundation for the structural control and design of novel copolymers.
The cyclic-stretching induced phase transition of a butene/ethylene copolymer containing 1.5%(mole fraction) co-units was explored with mechanical testing and wide angle X-ray diffraction,and the mechanical performance was correlated with phase transition kinetics.The results show that during the initial stretching,the phase transition was triggered with yielding.On the other hand,during the recovery and secondary stretching,the phase transition was independent of yielding.However,the phase transition kinetics can be significantly accelerated when the stretching strength exceeds the stress of the initial yielding.Moreover,the correspondence between the mechanical properties and the FormⅠ fraction indicates a stress-dominant mechanism for the phase transition.The results shed light on the relationship between macroscopic mechanical properties and microscopic crystalline structures and provide the foundation for the structural control and design of novel copolymers.
引文
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[2]Azzurri F,Flores A,Alfonso G C,et al.Polymorphism of isotactic poly(1-butene)as revealed by microindentation hardness.1.Kinetics of the transformation[J].Macromolecules,2002,35(24):9069-9073.
[3]Azzurri F,Flores A,Alfonso G C,et al.Polymorphism of isotactic polybutene-1 as revealed by microindentation hardness.Part II:Correlations to microstructure[J].Polymer,2003,44(5):1641-1645.
[4]Rosa C D,Auriemma F,Ballesteros O R D,et al.Crystallization properties and polymorphic behavior of isotactic poly(1-butene)from metallocene catalysts:The crystallization of FormⅠfrom the melt[J].Macromolecules,2009,42(21):33-41.
[5]Liu Y,Cui K,Tian N,et al.Stretch-induced crystalcrystal transition of polybutene-1:An in situ synchrotron radiation wide-angle X-ray scattering study[J].Macromolecules,2012,45(6):2764-2772.
[6]He L,Wang B,Yang F,et al.Featured crystallization polymorphism and memory effect in novel butene-1/1,5-hexadiene copolymers synthesized by post metallocene hafnium catalyst[J].Macromolecules,2016,49(17):6578-6589.
[7]Natta G,Corradini P,Bassi I W.Crystal structure of isotactic poly-alpha-butene[J].II Nuovo Cimento,1960,15(1):52-67.
[8]Jones A T.Polybutene-1-typeⅡcrystalline form[J].Journal of Polymer Science Part B Polymer Letters,1963,1(8):455-456.
[9]Holland V F,Miller R L.Isotactic polybutene-1 single crystals:Morphology[J].Journal of Applied Physics,1964,35(11):3241-3248.
[10]Boor Jr J,Youngman E A.Polymorphism in poly-1-butene:Apparent direct formation of modificationⅠ[J].Journal of Polymer Science Part A Polymer Chemistry,1964,2(9):903-907.
[11]Danusso F,Gianotti G.Isotactic polybutene-1:Formation and transformation of modification 2[J].Macromolecular Chemistry&Physics,1965,88(1):149-158.
[12]Tashiro K,Hu J,Wang H,et al.Refinement of the crystal structures of FormsⅠandⅡof isotactic polybutene-1 and a proposal of phase transition mechanism between them[J].Macromolecules,2016,49(4):1392-1404.
[13]Hu J,Tashiro K.Relation between higher-order structure and crystalline phase transition of oriented isotactic poly-butene-1 investigated by temperaturedependent time-resolved simultaneous WAXD/SAXSmeasurements[J].Polymer,2016,90:165-177.
[14]Qiao Y,Wang Q,Men Y.Kinetics of nucleation and growth of FormⅡtoⅠpolymorphic transition in polybutene-1 as revealed by stepwise annealing[J].Macromolecules,2016,49(14):5126-5136.
[15]Weynant E,Haudin J M,G'sell C.Plastic deformation and solid-phase transformation in polybutene-1[J].Journal of Materials Science,1982,17(4):1017-1035.
[16]Goldbach V G.Zur Umwandlung der polymorphen struktur von polybuten-1 unter der wirkung mechanischer spannungen[J].Macromolecular Materials&Engineering,2010,29(1):213-227.
[17]Goldbach V G.Spannungsinduzierte modifikationsumwandlungⅡnachⅠvon polybuten-1[J].Macromolecular Materials&Engineering,1974,39(1):175-188.
[18]Asada T,Sasada J,Onogi S.Rheo-optical studies of high polymers.XXI.The deformation process and crystal transformation in polybutene-1[J].Polymer Journal,1972,3(3):350-356.
[19]Tanaka A,Sugimoto N,Asada T,et al.Orientation and crystal transformation in polybutene-1 under stress relaxation[J].Polymer Journal,1975,7(5):529-537.
[20]Maruyama M,Sakamoto Y,Nozaki K,et al.Kinetics study of theⅡ-Ⅰphase transition of isotactic polybutene-1[J].Polymer,2010,51(23):5532-5538.
[21]Cavallo D,Kanters M J W,Caelers H J M,et al.Kinetics of the polymorphic transition in isotactic poly(1-butene)under uniaxial extension:New insights from designed mechanical histories[J].Macromolecules,2014,47(9):3033-3040.