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山东省烯烃催化与聚合重点实验室 橡塑材料与工程教育部重点实验室 青岛科技大学高分子科学与工程学院 青岛 266042
Published:2018-6,
Received:27 November 2017,
Revised:25 January 2018,
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Yi Zou, Chen-guang Liu, Ai-hua He. Isothermal Crystallizations of Polybutene-1 and Polybutene-1 Alloy from Their Solutions. [J]. Acta Polymerica Sinica 0(6):765-772(2018)
Yi Zou, Chen-guang Liu, Ai-hua He. Isothermal Crystallizations of Polybutene-1 and Polybutene-1 Alloy from Their Solutions. [J]. Acta Polymerica Sinica 0(6):765-772(2018) DOI: 10.11777/j.issn1000-3304.2017.17322.
研究了聚丁烯-1 (PB-1)及聚丁烯合金(PBA)中PB-1的溶液等温结晶行为. 测定了PB-1在正庚烷溶剂中的溶解度曲线,采用膨胀计法研究了PB-1和PBA中PB-1组分的溶液等温结晶动力学. 研究发现,等温结晶温度的升高会降低PB-1的结晶速率,但不影响PB-1在溶液中的结晶成核方式;PBA中PB-1组分的溶液等温结晶速率更快,聚丙烯(PP)组分的存在改变了PB-1的结晶成核方式. 示差扫描量热仪(DSC)和广角X射线衍射仪(WAXD)测试表明PB-1的溶液等温结晶形成I′和III晶型,结晶温度的提高与PP组分的存在都会促进PB-1晶型III的产生.
It is known that the solubility of PB-1 in
n
-heptane correlates closly to temperature
so it is thus of vital importance to investigate the solution crystallization of polybutene-1 (PB-1) and polybutene-1 in-reactor alloy (PBA)
via
the cooling solution crystallization method. In this work
the isothermal solution crystallization behaviors of PB-1 and PB-1 in-reactor alloy (PBA) from
n
-heptane were investigated. The dissolution temperature and isothermal crystallization temperature were determined from the solubility curves of PB-1 in
n
-heptane obtained by grametry. The isothermal crystallization kinetics of PB-1 and PBA from solutions were studied by dilatometry. The solution crystallization rate decreased with increasing isothermal temperature without changing the nucleation mode of PB-1. However
the crystallization rate of PB-1 component in PBA was faster than that of pure PB-1. The presence of polypropylene (PP) component in PBA shortened nucleation induction period of PB-1 component
and PB-
b
-PP copolymer could accelerate crystallization rate of PB-1 component. Additionally
the DSC test confirmed that the crystal form I′ and III of PB-1 were generated during the solution crystallization in both pure PB-1 and PBA
and no crystal form transformation occurred at room temperature. Due to the solvation of
n
-heptane
the two crystal forms I and II of PB-1 were not observed in this system. From WAXD measurement
it has also been found that the increase in solution crystallization temperature promoted the relative content of the crystal form III with a decrease in the crystallinity of PB-1. This was because that the increase in temperature led to decrease in supersaturation of solution system
which weakened the driving force of the crystallization and decreased the crystallizable component of PB-1. The behavior change of PB-1 component in PBA with temperature was similar to that of pure PB-1. At the same temperature
the presence of PP component in PBA promoted the III/I′ ratio and the crystallinity of PB-1. We further proposed the crystallization models for PB-1 and PBA in solutions.
聚丁烯聚丁烯合金溶解度溶液结晶等温结晶动力学
Polybutene-1Polybutene-1 alloySolubilitySolution crystallizationIsothermal crystallization kinetics
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