Macrocyclic arylene ether ether sulfide oligomers: New intermediates for the synthesis of high-performance poly(arylene ether ether sulfide)s

被引:32
作者
Wang, YF [1 ]
Hay, AS [1 ]
机构
[1] MCGILL UNIV,DEPT CHEM,MONTREAL,PQ H3A 2K6,CANADA
关键词
D O I
10.1021/ma961044o
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A convenient and efficient synthetic route to a new class of macrocyclic aryl ether ether sulfide oligomers is described. This new class of cyclic oligomers is prepared, in excellent yield, by quantitative chemical reduction of macrocyclic aryl ether ether sulfoxide oligomers with oxalyl chloride and tetrabutylammonium iodide. The cyclic sulfoxide oligomeric precursors are prepared in high yield by an aromatic nucleophilic substitution reaction from bis(4-fluorophenyl) sulfoxide and potassium salts of bisphenols under high-dilution conditions. These novel cyclic oligomers were characterized by a combination of GPC, NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF-MS), and thermal analyses. The cyclic nature of these oligomers was confirmed by NMR and MALDI-TOF-MS analyses of cyclic sulfoxide oligomers 4a and its linear oligomers 6 and 7. The cyclic sulfoxide oligomers are amorphous with T(g)s varying from 140 to 199 degrees C. Upon chemical reduction, the corresponding sulfide oligomers are highly crystalline with T-m varying from 237 to 350 degrees C. The quantitative reduction of the cyclic sulfoxide oligomers to cyclic sulfide oligomers was confirmed by NMR and MALDI-TOF-MS analyses of sulfoxide 4c and its corresponding sulfide 5c. Ring-opening polymerization (ROP) of the cyclic aryl ether ether sulfide oligomers to corresponding high molecular weight linear polymers can be effected in the melt phase with the addition of a catalytic amount of 2,2'-dithiobis-(benzothiazole) (DTB) disulfide. A tough semicrystalline polymer obtained from ROP of 5a has a T-g of 150 degrees C and T-m of 313 degrees C.
引用
收藏
页码:182 / 193
页数:12
相关论文
共 37 条
[1]   SYNTHESIS AND PROPERTIES OF POLYARYLETHERKETONES [J].
ATTWOOD, TE ;
DAWSON, PC ;
FREEMAN, JL ;
HOY, LRJ ;
ROSE, JB ;
STANILAND, PA .
POLYMER, 1981, 22 (08) :1096-1103
[2]   MASS-SPECTROMETRY OF SYNTHETIC-POLYMERS BY UV MATRIX-ASSISTED LASER DESORPTION IONIZATION [J].
BAHR, U ;
DEPPE, A ;
KARAS, M ;
HILLENKAMP, F ;
GIESSMANN, U .
ANALYTICAL CHEMISTRY, 1992, 64 (22) :2866-2869
[3]  
BAU JR, 1994, POLYMER, V35, P4949
[4]  
Beavis R C, 1989, Rapid Commun Mass Spectrom, V3, P233, DOI 10.1002/rcm.1290030708
[5]  
BRUNELLE DJ, 1993, RING OPENING POLYM M, pCH11
[6]   ARYL FLUORIDE MONOMERS IN NUCLEOPHILIC AROMATIC-SUBSTITUTION POLYMERIZATION - EVALUATION OF MONOMER REACTIVITY BY F-19 NMR-SPECTROSCOPY [J].
CARTER, KR .
MACROMOLECULES, 1995, 28 (19) :6462-6470
[7]   CONVENIENT SYNTHESIS AND FACILE POLYMERIZATION OF CYCLIC ARYL ETHER KETONES CONTAINING THE 1,2-DIBENZOYLBENZENE MOIETY [J].
CHAN, KP ;
WANG, YF ;
HAY, AS .
MACROMOLECULES, 1995, 28 (02) :653-655
[8]   SYNTHESIS AND CHARACTERIZATION OF NOVEL CYCLIC (ARYL ETHER KETONE)S, CYCLIC (ARYL ETHER PHTHALAZINE)S, AND CYCLIC (ARYL ETHER ISOQUINOLINE)S [J].
CHAN, KP ;
WANG, YF ;
HAY, AS ;
HRONOWSKI, XPL ;
COTTER, RJ .
MACROMOLECULES, 1995, 28 (20) :6705-6717
[9]  
CHAN KP, 1995, POLYM PREPR AM CHEM, V36, P132
[10]   SYNTHESIS, STRUCTURE, AND RING-OPENING POLYMERIZATION OF STRAINED MACROCYCLIC BIARYLS - A NEW ROUTE TO HIGH-PERFORMANCE MATERIALS [J].
COLQUHOUN, HM ;
DUDMAN, CC ;
THOMAS, M ;
OMAHONEY, CA ;
WILLIAMS, DJ .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1990, (04) :336-339