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辛雁

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单链和寡链等规聚苯乙烯聚集体的结晶行为
2005年
Single- and a few-chain aggregates of isotactic polystyrene(i-PS) were prepared by the freeze-drying procedure from dilute solutions with the concentration from 1×10-3 to 2×10-5 g/mL.It was found that the melting point of crystals was gradually shifted to lower temperatures as the solution concentration decreased by the differential scanning calorimetry(DSC).As a result, the thickness of the lamellas of bulk samples and the samples prepared by the freeze-drying procedure from 2×10-5 g/mL solution decreased from 19.3 nm to 12.6 nm,respectively.The half crystallization time(t1/2) of samples by freezing-dried from 1×10-4 g/mL solution was about 36 s,it was merely a tenth of the period of the bulk sample annealed at 468.3 K.In addition,the growth rate of spherulite(dr/dt) of the samples prepared from 2×10-5 g/mL solution was more faster than ones of the bulk samples annealed at 478.3 K.All these should be attributed to the samples with less entanglement prepared by freeze-drying procedure from dilute solution.A preliminary study on the crystallization of the samples indicates that entanglements has a pronounced effect on crystallization behavior of polymer.
辛雁于瀛何勇张宇范仲勇
关键词:等规聚苯乙烯单链寡链
链缠结对等规聚苯乙烯结晶的影响
2006年
在1×10-3-2×10-5 g·mL-1溶液浓度范围内,用溶液雾化冷冻升华法制备了等规聚苯乙烯(i-PS)的单链、寡链非晶态聚集体.随着溶液浓度降低,i-PS分子链团间的分离程度增大,链间缠结随之减少,因此冷冻升华制备的样品中单、寡链线团数目逐渐增多.DSC研究结果表明随着溶液浓度的降低,冷冻升华样品的结晶温度逐渐降低;等温结晶得到的晶粒熔点和结晶度降低.由浓度为2×10-5 g·mL-1溶液制备的i-PS样品在468.3 K熔体结晶60 min后,得到平均体积约为1.5×104 nm3的单链晶粒.用SEM观察到晶粒尺寸约为20-50 nm.采用偏光显微镜(POM)测量了不同温度等温时i-PS单、寡链聚集体球晶的生长速率.用Hoffmann理论进行了描述,计算得到了i-PS单链聚集体熔体结晶片晶的端表面能(σe)为30.2 erg·cm-2,侧表面能(σ)为5.7 erg·cm-2及单分子链折叠功(q)约为4.5×10-13 erg·molecule-1.与文献值相比,实验结果表明链缠结对聚合物结晶有很大影响.
于瀛辛雁何勇周之怡范仲勇
关键词:等规聚苯乙烯
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