冰片烯-二氧化硫聚砜树脂的合成及表征

摘要

Bomylene-sulfurdioxide polysulfone resin( BE-SO2 )was synthesized by free radical copolymerization of monomers SO2 and bomylene (BE) which synthesized from α-pinene. Similarly, BE-SO2-Ma and BE-SO2-St were synthesized using BE,SO2, maleie anhydride (MA) as monomers and BE, SO2, styrene (St) as monomers respectively. Effects of operating conditions such as monomer ratio, polymerization temperature and reaction time on the copolymer yields are discussed. The results showed that the optimum reaction conditions are as follows∶ reaction temperature -20 ℃, reaction time 4 h, n(BE) 1 mmol, n(BE)∶n(Ma) 1∶ 1, n(BE)∶ n(St) 1∶ 1, CYC as solvent and volume 4 mL, and the highest yield of BE-SO2, BE-SO2-Ma, BE-SO2-St are 70 ％ ,64 ％ and 71％, respectively. The structure of the copolymers were characterized by FT-IR, GPC, DSC, EA and SEM. BE-SO2 was a black solid powder with weight average molecular weight( Mw) of 1 069, number average molecular weight (Mn ) of 376, and Tg of 134.5 ℃; BE-SO2-Ma polysulfone resin is a dark brown solid powder with Mw of 1 576, Mn of 402and Tg of 152.0 ℃; BE-SO2-St polysuffone resin is a tan solid powder with Mw of 33 054, Mn of 952 and Tg of 174.8 ℃.%以α-蒎烯为原料合成冰片烯.以冰片烯(BE)、二氧化硫(SO2)为单体,采用自由基聚合方法合成了冰片烯-二氧化硫聚砜树脂(BE-SO2),用同样的方法分别以冰片烯(BE)、二氧化硫(SO2)、马来酸酐为单体和以冰片烯(BE)、二氧化硫(SO2)、苯乙烯(St)为单体,合成冰片烯-二氧化硫-马来酸酐(BE-SO2-Ma)以及冰片烯-二氧化硫-苯乙烯(BE-SO2-St)两种三元共聚物.讨论了单体配比、聚合反应的温度和时间对共聚物得率的影响,结果表明:n(BE)1 mmol,n(BE):n(Ma)1:1,n(BE):n(St)1:1,加入4 mL CYC作溶剂,在-20℃条件下反应4 h,BE-SO2,BE-SO2-Ma,BE-SO2-St得率最高,分别为70%、64%和71%.此外,分别用FT-IR、GPC、DSC、EA和SEM等方法对共聚物结构进行了表征,BE-SO2为粉末状黑色固体,重均相对分子质量(Mw)为1069,数均相对分子质量(Mn)为376,Tg为134.5℃;BE-SO2-Ma共聚物为粉末状黑褐色固体,Mw为1 576,Mn为402,Tg为152.0℃;BE-SO2-St共聚物为粉末状黄褐色固体,Mw为33054,Mn为952,Tg为174.8℃.