溶剂性质对溶剂蒸气加速等规聚丁烯-1相转变的影响  

Influence of Solvent Type on Acceleration of Phase Transition from PhaseⅡto Phase I of Polybutene-1 via Solvent Vapor Treatment

作　　者：姜继超 宋新月 毛禹东 吴广峰[3] 张吉东[1,2] Ji-chao Jiang;Xin-yue Song;Yu-dong Mao;Guang-fengWu;Ji-dong Zhang(State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026;School of Chemistry Engineering,Changchun University of Technology,Changchun 130012)

机构地区：[1]中国科学院长春应用化学研究所,高分子物理与化学国家重点实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026 [3]长春工业大学化学与工程学院,长春130012

出　　处：《高分子学报》2022年第3期254-260,共7页Acta Polymerica Sinica

基　　金：吉林省科技发展计划项目(项目号20210201067GX)资助。

摘　　要：以50℃等温结晶后的等规聚丁烯-1(PB-1)为研究对象,利用X射线衍射(XRD)和示差扫描量热技术(DSC)对不同溶剂蒸气处理的PB-1进行分析,并用原位XRD在线研究了溶剂熏蒸聚丁烯-1的Ⅱ-Ⅰ相转变过程.XRD与DSC结果表明除了水和醇类溶剂,其他大多数溶剂如正己烷、三氯甲烷、1,2-二氯乙烷、苯、甲苯、二甲苯、氯苯、乙酸乙酯、四氢呋喃、丙酮溶剂对Ⅱ-Ⅰ相转变过程均有明显的促进作用,可以使常规条件下4~5天的相转变加速到几十分钟.通过原位XRD表征发现,溶剂熏蒸过程中聚丁烯-1的晶型转变过程为晶型Ⅱ消失的同时晶型I生成.溶剂进入样品内部促进晶型转变主要分为两步:吸附和扩散.吸附主要受溶解度参数和极性影响,水和乙醇等不良溶剂没有促进相变的效果;而扩散主要取决于溶剂分子的几何尺寸:单一方向的小尺寸更有利于进入样品内部,促进晶型转变.通过这个研究我们认为正己烷或石油醚是加速PB-1的Ⅱ-I相转变的高效低毒溶剂,具有潜在的应用前景.A series of isotactic polybutene-1(PB-1)in phaseⅡobtained via isothermal crystallization at 50℃were treated with different solvent vapors.Wide-anlge X-ray diffraction(WAXD)and differential scanning calorimetry(DSC)techniques were used to evaluate such samples before and after treatment.Meanwhile,in situ XRD was used to study the phase transition process of PB-1 annealed in different solvent vapors.Solvents,except water and alcohol solvents,such as n-hexane,chloroform,1,2-dichloroethane,benzene,toluene,xylene,chlorobenzene,ethyl acetate,tetrahydrofuran,acetone have obvious accelerating effect on the phase transition process,which can shorten the phase transition time from more than 4-5 days under normal conditions to tens of minutes.Through in situ XRD characterization,it was found that during the solvent annealing process,the crystal formⅡof PB-1 disappeared while the crystal form I was formed.The entrance of solvents,which promotes the crystal form transformation,can be divided into two steps:adsorption and diffusion.Adsorption is affected by solubility parameters and polarity,while diffusion mainly depended on the geometric size of solvent molecules:a small size in any direction will lead to a faster spread and larger promotion effect.Through this research,we found that n-hexane or petroleum ether is an efficient and low-toxic solvent that accelerates theⅡ-I phase transition of PB-1,and has good application prospects.

关 键 词：等规聚丁烯-1 晶型转变 溶剂蒸气退火 X射线衍射 

分 类 号：TQ325.15[化学工程—合成树脂塑料工业]