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第 8 期                    刘金才,等:  聚苯乙烯为规整侧链的支化 SIS 的设计及合成                                ·1707·


            制备支化结构的 SIS 在相对分子质量、相对分子质                          [5]   Cowie  J.  Block  and  graft  copolymer  in  comprehensive  polymer
            量分布与组分含量相似的情况下,在相同的测试温                                 science:  The  synthesis,  characterization,  reactions  &  application  of
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            度与频率时支化结构聚合物的黏度要低于线型结构                             [6]   Hadjichristidis N, Latrou H, Pitsikalis M. Macromolecular architectures
            的聚合物。这可能是由于在相同相对分子质量的情                                 by  living  and  controlled/living  polymerizations[J].  Progress  in
                                                                   Polymer Science, 2006, 31(2): 1068-1132.
            况下,支化结构的分子链要短于线型结构的分子链,
                                                               [7]   Uhrig D, May J M. Synthesis of combs, centipedes, and barbwires:
            侧链聚苯乙烯的相对分子质量远小于聚苯乙烯链缠                                 Poly(isoprene-graft-styrene)  regular  multigraft  copolymers  with
            结的临界相对分子质量(M c )35000,从而支化聚合                           trifunctional,  tetrafunctional,  and  hexafunctional  branch  points[J].
                                                                   Macromolecules, 2002, 35: 7182-7190.
            物链之间的缠结程度小,黏度也相应较低                    [19] 。另一     [8]   Vazaios  A,  Hadjichristidis  N.  Anionic  polymerization  of
            方面,可能由于短聚苯乙烯侧链的存在使聚合物分                                 styrenicmacromonomers  of  polyisoprene,  polybutadiene,  and
            子链间的距离增大,分子链在相对运动时受到的摩                                 polystyrene[J].  Journal  of  Polymer  Science,  Part  A:  Polymer
                                                                   Chemistry, 2005, 43: 1038-1048.
            擦阻力减小,从宏观上表现为黏度降低。此外,还                             [9]   Rangou  S,  Avgeropoulos  A.  Synthesis  of  dendritic  terpolymers
            可以看出,线型 SIS 聚合物的熔体黏度对切变速率                              consisting  of  polystyrene,  polybutadiene,  and  polyisoprene  with
            更具有依赖性,黏度的降低随切变速率下降得更加                                 different isomerisms[J]. Journal of Polymer Science, Part A: Polymer
                                                                   Chemistry, 2009, 47(6): 1567-1574.
            明显,这说明线型 SIS 较支化 SIS 链缠结多,随着                       [10]  Percee V, Rinaldi P L, Auman B C. Comb-like polymers and graft
            切变速率的增大,链缠结引起黏度降低得越明显。                                 copolymers  from  macromers[J].  Polymer  Bulletin,  1983,  10(5/6):
                                                                   215-222.
            3   结论                                             [11]  Schulz G O, Milkovich R. Styrene/isoprene diblock macromere graft
                                                                   copolymer:  synthesis  and  properties[J].  Industrial  &  Engineering
                                                                   Chemistry Poduct Research and Development, 1986, 25(2): 148-152.
                (1)采用负离子聚合法,经一步封端成功合成                          [12]  Wang W W, Wang W Y, Mays J, et al. Synthesis and characterization
            出了相对分子质量在 3000~5000 的聚苯乙烯大分子                           of  graft  copolymers  poly(isoprene-g-styrene)  of  high  molecular
            单体,相对分子质量可控,封端效率﹥95%。                                  weight  by  a  combination  of  anionic  polymerization  and  emulsion
                                                                   polymerization[J].  Industry  &  Engineering  Chemistry  Research,
                (2)利用聚苯乙烯大分子单体通过一锅法成功                              2015, 54(4): 1292-1300.
            合成出了相对分子质量为 10 万~14 万,相对分子质                        [13]  Driva  P,  Latrou  H,Nikos  H,  et al.  Anionic  homo-  and
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            量分布小于 1.2 的聚苯乙烯为规整侧链的支化结构
                                                                   macromolecular  architectures[J].  Journal  of  Polymer  Science,  Part
            SIS,为制备窄分布的支化聚合物提供了新思路。                                A:Polymer Chemistry, 2005, 43(18): 4070-4078.
                (3)制备的支化结构 SIS 的熔体黏度要明显低                       [14]  Nikopoulou  A,  Latrou  H,  Nikos  H,  et al.  Anionic  homo-  and
                                                                   copolymerization of styrenic triple-tailed polybutadienemacromonomers[J].
            于相似结构参数的线型 SIS,可实现低加工温度的
                                                                   Journal  of  Polymer  Science,  Part  A:  Polymer  Chemistry,  2007,
            设想,有望在与塑料等共混改性时降低加工成本。                                 45(16): 3513-3523.
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