HETEROLYTIC BROMINATION OF POLYSTYRENE IN HOMOGENEOUS PHASE .2. KINETICS OF BROMINATION CATALYZED BY SNCL4, SBCL5 AND TICL4

被引：6

作者：

CAMPS, M ^{[1
]}

MONTHEARD, JP ^{[1
]}

BENROKIA, F ^{[1
]}

机构：

[1] FAC SCI & TECH ST ETIENNE, CHIM ORGAN & MACROMOLEC LAB, F-42023 ST ETIENNE 2, FRANCE

来源：

EUROPEAN POLYMER JOURNAL | 1991年 / 27卷 / 4-5期

关键词：

D O I：

10.1016/0014-3057(91)90194-S

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The bromination of polystyrene (PS) by Br2 has been studied kinetically in the homogeneous liquid phase. The catalysts were the Lewis acids (AL) SnCl4, SbCl5 and TiCl4. The rate is expressed as k4[AL]-alpha-[Br2]3[PS] where alpha = 1.22, 1.25 and 2.0 for SbCl5, TiCl4 and SnCl4 respectively. The rate constant k4 increases with the proportion of CH2Cl2 in the mixture cyclohexane/CH2Cl2. The reactivity of PS is very close to that of cumene according to our kinetic measurements. No "neighbouring group effect" has been found. The presence of a brominated unit has no effect on the reactivity of a nearby styrene unit. A mechanism of bromination is proposed.

引用

页码：389 / 396

页数：8

共 59 条

[1] KINETICS OF HIGH-POLYMER REACTIONS - EFFECTS OF NEIGHBORING GROUPS [J].

ALFREY, T ;

LLOYD, WG .

JOURNAL OF CHEMICAL PHYSICS, 1963, 38 (02) :318-&

[2] THE KINETICS OF THE ZINC CHLORIDE-CATALYZED BROMINATION OF POLYMETHYLBENZENES IN ACETIC ACID SOLUTION [J].

ANDREWS, LJ ;

KEEFER, RM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1956, 78 (18) :4549-4553

[3]

ARRANZ F, 1969, REV PLAST MOD, V20, P1

[4]

BAILAR JC, 1973, COMPREHENSIVE INORGA, P1344

[5]

BENHAM JL, 1989, CHEM REACTIONS POLYM

[6] ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS [J].

BERLINER, E .

PROGRESS IN PHYSICAL ORGANIC CHEMISTRY, 1964, 2 :253-321

[7] INFRARED-SPECTRA OF UNIFORMLY CHLOROSULFONYL-SUBSTITUTED STYRENE DIVINYLBENZENE RESINS [J].

BOGOCZEK, R ;

KOCIOLEK-BALAWEJDER, E .

REACTIVE POLYMERS, 1987, 7 (01) :57-62

[8] REACTION-KINETICS OF POLYMER SUBSTITUENTS - NEIGHBORING-SUBSTITUENT EFFECTS IN SINGLE-SUBSTITUENT REACTIONS [J].

BOUCHER, EA .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1972, 68 (12) :2295-&

[9] TRIFLUOROACETIC ACID AS A MEDIUM FOR ELECTROPHILIC SUBSTITUTION REACTIONS . RATES AND ISOMER DISTRIBUTIONS FOR BROMINATION NITRATION AND MERCURATION OF BENZENE AND TOLUENE IN TRIFLUOROACETIC ACID [J].

BROWN, HC ;

WIRKKALA, RA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (07) :1447-&

[10]

BUTLER JM, 1951, Patent No. 2572557

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