丙烯酰氯对丁苯共聚物活性链偶联反应的研究

以n BuLi为引发剂 ,四氢呋喃 (THF)为调节剂 ,抽余油为溶剂 ,采用丙烯酰氯为偶联剂对丁二烯 苯乙烯阴离子共聚体系进行偶联反应 ,研究了影响偶联反应的各种因素 ,如偶联剂用量、相对分子质量、偶联反应时间、偶联反应温度、THF用量、末端基团、单体浓度等 ;确定了偶联剂用量与聚合物相对臂数之间的关系及其偶联效率 .

COUPLING REACTION OF LIVING BUTADIENE-STYRENE COPOLYMER WITH ACRYLOYL CHLORIDE

The coupling reaction of butadiene styrene anionic living coploymerization system with acryloyl chloride(AC) in extracted oil have been studied.Various factors related to the coupling reaction,such as AC/BuLi(mole ratio),reaction time,reaction temperature,relative molecular weight of the living copolymer,amount of THF,end group of the living copolymer,monomer concentration,were investigated.Coupling efficiency and branching number were dramatically effected by AC/BuLi(mole ratio);when 0 7≤AC/BuLi≤10,the coupling efficiency was higher than 50% and the average branching number was higher than 3;while AC/BuLi was less than 0 7 or higher than 10,the obtained polymer was with poor coupling efficiency and the branching number was decreased.Coupling efficiency was decreased when the molecular weight of living copolymer or the temperature of coupling reaction was increased;coupling efficiency was increased while the time of coupling reaction or the amount of THF was increased;the monomer concentration was little effect on coupling efficiency;when the end group of the living copolymer was butadiene,the resulted polymer was with higher coupling efficiency but lower branching number;when the end group of the living copolymer was styrene,the obtained polymer was with lower coupling efficiency but higher branching number.The optimism conditions of the coupling reaction were established,that is AC/BuLi=0 7～10(mole ratio),reaction time 60 min,reaction temperature 50～70℃,THF/BuLi≤50(mole ration),M]=11 wt%,the branching number and the coupling efficiency of the obtained polymer were 2 3～8 0 and 50%～80% respectively.