Synthesis of electron-rich versus electron-poor poly {[1,4-phenylene]-[1-(n-alkylsulfinyl)ethylene]}s via the sulfinyl precursor route in different organic solvents

被引:18
作者
Adriaensens, P [1 ]
Van der Borght, M [1 ]
Hontis, L [1 ]
Issaris, A [1 ]
van Breemen, A [1 ]
de Kok, M [1 ]
Vanderzande, D [1 ]
Gelan, J [1 ]
机构
[1] Univ Limburg, Div Chem, Inst Mat Res, Lab Organ & Polymer Chem, B-3590 Diepenbeek, Belgium
关键词
poly(phenylene vinylene)s; synthesis; polymerisation mechanism;
D O I
10.1016/S0032-3861(00)00071-9
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
In this paper new insights in the mechanism of the sulfinyl precursor route towards poly(phenylene vinylene) (PPV) derivatives are presented by studying the polymerisation reaction in various solvents and by evaluating the influence of both electron donating and withdrawing substituents. A strong indication is presented that in alcohols the expulsion of the leaving group is involved in the rate determining step of the reaction, the formation of the p-quinodimethane intermediate, which further also depends on the type of solvent and substituents. Moreover, two polymerisation mechanisms can occur simultaneously: a radical mechanism that results in high molecular weight polymers and an anionic mechanism yielding low molecular weights. Competition between both mechanisms strongly depends on the solvent and type of substituents. (C) 2000 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:7003 / 7009
页数:7
相关论文
共 27 条
[1]   LIGHT-EMITTING-DIODES BASED ON CONJUGATED POLYMERS [J].
BURROUGHES, JH ;
BRADLEY, DDC ;
BROWN, AR ;
MARKS, RN ;
MACKAY, K ;
FRIEND, RH ;
BURN, PL ;
HOLMES, AB .
NATURE, 1990, 347 (6293) :539-541
[2]   Kinetics of polymerization reaction of α,α′-bis(tetrahydrothiophenio)-p-xylene dichloride [J].
Cho, BR ;
Kim, YK ;
Han, MS .
MACROMOLECULES, 1998, 31 (07) :2098-2106
[3]   MECHANISM OF POLYMERIZATION OF ALPHA,ALPHA'-BIS(TETRAHYDROTHIOPHENIO)-P-XYLENE DICHLORIDE [J].
CHO, BR ;
HAN, MS ;
SUH, YS ;
OH, KJ ;
JEON, SJ .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (06) :564-566
[4]   THE EFFECT OF RADICAL TRAPPING REAGENTS UPON FORMATION OF POLY(ALPHA-TETRAHYDROTHIOPHENIO PARA-XYLYLENE) POLYELECTROLYTES BY THE WESSLING SOLUBLE PRECURSOR METHOD [J].
DENTON, FR ;
LAHTI, PM ;
KARASZ, FE .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 1992, 30 (10) :2223-2231
[5]   Electroluminescence in conjugated polymers [J].
Friend, RH ;
Gymer, RW ;
Holmes, AB ;
Burroughes, JH ;
Marks, RN ;
Taliani, C ;
Bradley, DDC ;
Dos Santos, DA ;
Brédas, JL ;
Lögdlund, M ;
Salaneck, WR .
NATURE, 1999, 397 (6715) :121-128
[6]  
GARAY R, 1989, MAKROMOL CHEM S, V5, P1
[7]   POLYMERIZATION OF ALPHA-HALOGENATED P-XYLENES WITH BASE [J].
GILCH, HG ;
WHEELWRIGHT, WL .
JOURNAL OF POLYMER SCIENCE PART A-1-POLYMER CHEMISTRY, 1966, 4 (6PA1) :1337-+
[8]   EFFICIENT LIGHT-EMITTING-DIODES BASED ON POLYMERS WITH HIGH ELECTRON-AFFINITIES [J].
GREENHAM, NC ;
MORATTI, SC ;
BRADLEY, DDC ;
FRIEND, RH ;
HOLMES, AB .
NATURE, 1993, 365 (6447) :628-630
[9]   Radical as well as anionic polymerisation mechanisms in the synthesis of poly(p-arylene vinylene) precursors [J].
Hontis, L ;
Van der Borght, M ;
Vanderzande, D ;
Gelan, J .
POLYMER, 1999, 40 (23) :6615-6617
[10]   Polymerization of a p-quinodimethane derivative to a precursor of poly(p-phenylene vinylene) - Indications for a free radical mechanism [J].
Issaris, A ;
Vanderzande, D ;
Gelan, J .
POLYMER, 1997, 38 (10) :2571-2574