NOVEL HIGH PERFORMANCE POLYMER"POLYSULFOXIMINE"

新型高性能聚合物“聚亚磺酰亚胺”

• 批准号: 07555596
• 负责人: TAKATA Toshikazu
• 金额: $ 0.83万
• 依托单位: OSAKA PREFECTURE UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555596/
• 关键词: POLYSULFOXIMINE; FRIEDEL-CRAFTS REACTION; POLYCONDENSATION; THERMAL STABILITY; SULFUR-CONTAINING POLYMER; HIGH PERFORMANCE POLYMER; SULFONIMIDOYL CHLORIDE; Friedel-Crafts重合; 塩化第二鉄; 溶解性; 含硫黄高分子

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

主链中含有亚磺酰亚胺部分的聚合物除了具有良好的热性能和机械性能外，还有望表现出氮原子上的取代基所具有的受控物理性能。然而，到目前为止，还没有聚亚磺酰亚胺的报道。最近，我们以三氯化铁催化N-甲苯磺酰基-4-苯氧基苯亚磺酰氯的傅克缩聚反应成功合成了聚亚磺酰亚胺（N-Ts衍生物），即10mol%三氯化铁的缩聚反应在硝基苯中120℃反应48h，得到80%相应的聚亚磺酰亚胺。通过核磁共振谱确定了聚合物的结构，其中聚亚磺酰亚胺的碳信号数减少到了8个，尽管单体的氢原子数降低了。磺酰亚胺酰氯为 12，表明缩聚反应仅发生在苯环的对位。通过用浓硫酸处理，将 N-Ts 衍生物转化为相应的 N-未取代衍生物（N-H 衍生物）。氢氧化钠的转化率为 80%。N-H 衍生物与烷基卤化物（例如氯化苄）在碱存在下反应，以适度的转化得到 N-烷基化产物（N-R 衍生物）。这些聚亚磺酰亚胺（N-Ts、N-H）的热稳定性，和通过热重分析和差异扫描量热法检查N-R衍生物）。N-TS和N-H衍生物非常稳定，显示出300 c左右的高玻璃过渡温度，而N-BN（N-苯甲酰基）低玻璃化转变温度（69°C）。与聚砜的玻璃化转变温度和失重温度相比，N-H衍生物的热稳定性最高。对聚亚磺酰亚胺（N-Ts衍生物）结构的详细研究表明：与完全对位取代的聚亚磺酰亚胺相比，该聚合物有时表现出相当复杂的核磁共振谱。在不同温度、催化剂浓度、溶剂和反应时间下，详细研究了亚磺酰氯与芳烃的缩合反应。结果表明，在该条件下会发生一些副反应，如IPSO取代磺酰亚胺酰氯的硫键苯碳，得到联苯衍生物作为对甲苯磺酰胺以外的产物。在某些情况下，联苯部分会作为主链骨架参与其中。

项目成果

Mami Ohno: "Syn Heri and Propertier of Poly (arylene eHer-lcetone) S" React. Funct. Polym.30・1-3. 149-156 (1996)

Mami Ohno：“Syn Heri 和聚（亚芳基 eHer-lcetone）S 的特性”Polym.30・1-3（1996）。

Mami Ohno: "Synthesis and Properties of Poly(aryleneltter-Ketines・・・)" React.Funct.Polym.30・1〜3. 149-156 (1996)

大野麻美：“聚(亚芳基酮-酮类化合物的合成和性能...)”React.Funct.Polym.30・1～3（1996）。

MASAMI KANAMARU,TOSHIKAZU TAKATA,TAKESHI ENDO: "SEQUENCE CHANGE OF POLY (N-ACYLURETHANE) S BASED ON TRANSESTERIFICATION" MACROMOL.CHEM.PHYS. 197 (6). 1795-1804 (1996)

Masami Kanamaru、Toshikazu TAKATA、Takeshi Endo：“基于酯交换的聚（N-酰基氨基甲酸酯）S 的序列变化” MACROMOL.CHEM.PHYS。

TOSHIKAZU TAKATA,KAZUAKI NAKAMURA,TAKESHI ENDO POLYSULFOXIMINE: "A NOVEL CLASS OF SULFUR-CONTAINING POLYMER" MACROMOLECULES. 29 (6). 2315-2317 (1996)

Toshikazu TAKATA、Kazuaaki Nakamura、Takeshi Endo 聚亚磺酰亚胺：“一类新型含硫聚合物”大分子。

Masami Kanamaru: "Sequence Change of Poly(N-acylurethane)s based on・・・" Macromol.Chem.Phys. 197・6. 1795-1804 (1996)

Masami Kanamaru：“基于……的聚（N-酰基氨基甲酸酯）的序列变化” Macromol.Chem.Phys 197・6 1795-1804（1996）