1996 Fiscal Year Final Research Report Summary
NOVEL HIGH PERFORMANCE POLYMER"POLYSULFOXIMINE"
| Project/Area Number |
07555596
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 試験 |
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| Research Field |
高分子合成
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| Research Institution | OSAKA PREFECTURE UNIVERSITY |
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Principal Investigator |
TAKATA Toshikazu OSAKA PREFECTURE UNIVERSITY,DEPARTMENT OF APPLIED CHEMISTRY,PROFESSOR, 工学部, 教授 (40179445)
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| Co-Investigator(Kenkyū-buntansha) |
TOGO Jyuzaemon NICCA CHEMICALS Co.LTD., RESEARCH DIVISION,HEAD, 研究開発本部, 本部長
NAKANISHI Saburo OSAKA PREFECTURE UNIVERSITY,DEPARTMENT OF APPLIED CHEMISTRY,ASSOCIATE PROFESSOR, 工学部, 助教授 (40081343)
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| Project Period (FY) |
1995 – 1996
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| Keywords | POLYSULFOXIMINE / FRIEDEL-CRAFTS REACTION / POLYCONDENSATION / THERMAL STABILITY / SULFUR-CONTAINING POLYMER / HIGH PERFORMANCE POLYMER / SULFONIMIDOYL CHLORIDE |
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| Research Abstract |
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
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