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

主链上有亚砜亚胺基团的聚合物除了具有良好的热性能和机械性能外，还有望表现出由氮原子上的取代基所引起的可控物理性能。然而，目前尚无聚亚砜亚胺的报道。摘要采用氯化铁催化n - toyl -4-苯氧苯-磺酰酰氯的frieel - crafts缩聚方法，在硝基苯中以10mol / l的氯化铁（120 C）缩聚48h，得到了相应的80%的聚亚砜亚胺（N-Ts衍生物）。聚合物结构经核磁共振谱测定，聚亚砜亚胺的碳信号数被还原为8个，而单体磺酰氯的碳信号数为12个，表明缩聚只发生在苯环对位上。通过CONC处理，将N-Ts导数转化为相应的n -未取代导数（N-H导数）。硫酸：更多的C酸和氢氧化钠在80%的转化率。n-h衍生物在碱的存在下与烷基卤化物（如氯化苄）反应，以中等转化率生成n -烷基化产物（n-r衍生物）。用热重分析和差示扫描量热法研究了这些聚亚砜亚胺（N-Ts、N-H和N-R衍生物）的热稳定性。N-Ts和N-H衍生物的玻璃化转变温度在300℃左右，而N-Bn （n -苄基）衍生物的玻璃化转变温度较低（69℃）。与聚砜相比，n-h衍生物在玻璃化转变温度和失重20%温度下的热稳定性最好。对聚亚砜亚胺（N-Ts衍生物）结构的详细研究表明，与完全对取代的聚亚砜亚胺相比，该聚合物有时表现出相当复杂的核磁共振谱。研究了磺胺酰氯与芳烃在不同温度、催化剂浓度、溶剂浓度和反应时间下的缩合反应。结果表明，在此条件下，磺胺酰氯的硫键苯碳发生了对邻基取代，得到了对甲苯磺酰胺以外的联苯衍生物。结果表明，在某些情况下，联苯基团会作为主链骨架参与。少

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。

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）

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。