NOVEL HIGH PERFORMANCE POLYMER"POLYSULFOXIMINE"

主链中含有磺基肟部分的聚合物除了具有良好的热性能和机械性能外，还有望显示出受控的物理性能，这是由氮原子上的取代基引起的。然而，到目前为止，还没有报道过聚磺基肟。最近，我们成功地将聚磺基肟进行了尺寸化氯化铁催化N-对甲苯磺酰基-4-苯氧基苯磺酰亚胺酰氯的Friedel-Crafts缩聚反应用10mol%的氯化铁在硝基苯中于120 ℃缩聚48 h，得到80%的相应聚磺酰亚胺，用核磁共振谱证实了聚合物的结构，虽然单体磺酰亚胺的HTAT为12，但聚磺酰亚胺的碳信号数减少到8。推测缩聚反应只发生在苯环的帕拉. N-Ts衍生物经浓硫处理后转化为相应的N-未取代衍生物（N-H衍生物 ...更多信息 在碱存在下，N-H衍生物与卤代烷烃如苄基氯反应生成N-烷基化产物（N-R衍生物）的热稳定性（N-Ts，N-H，N-Ts和N-R衍生物）的热重分析和差示扫描量热法测定。H衍生物是非常热稳定的，在300 ℃左右显示出高的玻璃化转变温度，而N-Bn（N-苄基）酮具有低的玻璃化转变温度（69 ℃）。N-H衍生物的玻璃化转变温度和失重20%的温度与聚砜相比，热稳定性最好。聚砜肟结构的详细研究（N-Ts衍生物）表明，与完全对位取代的聚磺酰亚胺相比，该聚合物有时显示出更为复杂的NMR谱.本文研究了磺酰亚胺酰氯与芳烃在不同温度下的缩合反应，研究了催化剂浓度、溶剂浓度和反应时间等因素对反应的影响，并提出了在此条件下进行一些副反应的建议，如磺酰亚胺酰氯中的硫键苯碳发生IPSO取代，生成对甲苯磺酰胺以外的联苯衍生物，结果表明，在某些情况下，联苯部分可能作为主链骨架参与反应。少

POLYMERS HAVING SULFOXIMINE MOIETY IN THE MAIN CHAIN ARE EXPECTED TO SHOW CONTROLLED PHYSICAL PROPERTIES WHICH WOULD BE CASED BY SUBSTITUENTS ON THE NITROGEN ATOM,IN ADDITION TO GOOD THERMAL AND MECHANICAL PROPERTIES.HOWEVER,NO POLYSULFOXIMINE HAS BEEN REPORTED SO FAR.RECENTLY,WE HAVE SUCCEEDED IN SYNTHESIZING POLYSULFOXIMINE (N-Ts DERIVATIVE) BY FERRIC CHLORIDE-CATALYZED FRIEDEL-CRAFTS POLYCONDENSATION OF N-TOSYL-4-PHENOXYBENZENE-SULFONIMIDOYL CHLORIDE,THE POLYCONDENSATION WITH 10 MOL% OF FERRIC CHLORIDEAT 120ﾟC FOR 48h IN NITROBENZENE AFFORDED 80% OF CORRESPONDING POLYSULFOXIMINE WAS OBTAINED.THE POLYMER STRUCTURE WAS DETERMINED BY THE NMR SPECTRA IN WHICH NUMBER OF CARBON SIGNALS OF POLYSULFOXIMINE WAS REDUCED TO 8, ALTHOUGH HTAT OF THE MONOMER SULFONIMIDOYL CHLORIDE WAS 12, SUGGESTING THE POLYCONDENSATION EXCLUSIVELY OCCURRED AT PARA POSITION OF THE BENZENE RING.THE N-Ts DERIVATIVE WAS CONVERTED TO THE CORRESPONDING N-UNSUBSTITUTED ONE (N-H DERIVATIVE) BY TREATING WITH CONC.SULFURI … More C ACID FOLLOWED BY SODIUM HYDROXIDE IN 80% CONVERSION.THE N-H DERIVATIVE REACTED WITH ALKYL HALIDES SUCH AS BENZYL CHLORIDE IN THE PRESENCE OF A BASE TO GIVE N-ALKYLATED PRODUCT (N-R DERIVATIVE) IN A MODERATE CONVERSION.THERMAL STABILITIES OF THESE POLYSULFOXIMINES (N-Ts, N-H,AND N-R DERIVATIVES) WERE EXAMINED BY THERMOGRAVIMETRIC ANALYSES AND DIFFERENTIAL SCANNING CALORIMETRY.N-Ts AND N-H DERIVATIVES WERE VERY THERMALLY STABLE SHOWING HIGH GLASS TRANSITION TEMPERATURES AROUND 300ﾟC,WHEREAS N-Bn (N-BENZYL) ONE HAD LOW GLASS TRANSITION TEMPERATURE (69ﾟC). THE N-H DERIVATIVE WAS MOST THERMALLY STABLE,BEING COMPARED TO POLYSULFONE IN GLASS TRANSITION TEMPERATURE AND TEMPERATURE WITH 20% WEIGHT LOSS.DETAILED STUDY ON THE STRUCTURE OF THE POLYSULFOXIMINE (N-Ts DERIVATIVE) INDICATED THAT THE POLYMER SOMETIMES SHOWED A RATHER COMPLICATED NMR SPECTRUM COMPARED WITH THE COMPLETELY PARA-SUBSTITUTED POLYSULFOXIMINE.THE CONDENSATION REACTION OF SULFONIMIDOYL CHLORIDE WITH ARENES WERE STUDIED IN DETAIL UNDER VARYING TEMPERATURE,CONCENTRATION OF CATALYST,SOLVENT,AND REACTION TIME.AS A RESULT,SOME SIDE REACTION WAS SUGGESTED TO TAKE PLACE UNDER THE CONDITIONS,SUCH AS IPSO SUBSTITUTION OF SULFUR-BONDED BENZENE CARBON OF SULFONIMIDOYL CHLORIDE,GIVING BIPHENYL DERIVATIVE AS A PRODUCT BESIDES PARA-TOLUENESULFONAMIDE.THE RESULTS CONCLUDE THAT THE BIPHENYL MOITY WOULD BE INVOLVED AS A MAIN CHAIN SKELETON IN SOME CASES. Less