Synthesis of well-defined functionalized polystyrenes with a definite number of chloromethylphenyl groups at chain ends or in chains by means of anionic living polymerization in conjunction with functional group transformation

被引:69
作者
Hirao, A [1 ]
Hayashi, M [1 ]
机构
[1] Tokyo Inst Technol, Dept Polymer Chem, Meguro Ku, Tokyo 1528552, Japan
关键词
D O I
10.1021/ma990618x
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 syntheses of well-defined polystyrenes functionalized with a definite number (from one to four) of chloromethylphenyl groups at the chain ends or in the chains by means of anionic Living polymerization in conjunction with functional group transformation are described. The synthetic method involves the introduction of anion-stable methoxymethylphenyl or tert-butyldimethylsilyloxymethylphenyl groups at the chain ends or in the chains and subsequent transformation reactions of these groups into chloromethylphenyl groups with BCl3. It is also possible to transform the tert-butyldimethylsilyloxymethylphenyl group into bromomethylphenyl and iodomethylphenyl groups by treatment with Me3SiCl-LiBr, and Me3SiCl-NaI, respectively. Furthermore, the synthesis of well-defined polystyrenes having two, four, and six methoxymethylphenyl and six chloromethylphenyl termini via a new iterative approach using 3-(tert-butyldimethylsilyloxy)-1-propyllithium is described. It involves repeated chemical transformations at the chain end from tert-butyldimethylsilyloxybutyl, bromobutyl, and methoxymethylphenyl groups to the chloromethylphenyl group. At each stage in the iteration, the number of chloromethylphenyl groups doubles. The resulting polymers all, after HPLC fractionation in some cases, possessed well-controlled molecular weights and narrow molecular weight distributions. Their functionalities were nearly quantitative in all cases.
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页码:6450 / 6460
页数:11
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共 41 条
[11]  
HEITZ T, 1988, MAKROMOL CHEM, V189, P777
[12]   Novel amphiphilic architectures by ring-opening metathesis polymerization of macromonomers [J].
Heroguez, V ;
Gnanou, Y ;
Fontanille, M .
MACROMOLECULES, 1997, 30 (17) :4791-4798
[13]   PROTECTION AND POLYMERIZATION OF FUNCTIONAL MONOMERS .18. SYNTHESES OF WELL-DEFINED POLY(VINYLPHENOL), POLY[(VINYLPHENYL)METHANOL], AND POLY[2-(VINYLPHENYL)ETHANOL] BY MEANS OF ANIONIC LIVING POLYMERIZATION OF STYRENE DERIVATIVES CONTAINING TERT-BUTYLDIMETHYLSILYL ETHERS [J].
HIRAO, A ;
KITAMURA, K ;
TAKENAKA, K ;
NAKAHAMA, S .
MACROMOLECULES, 1993, 26 (19) :4995-5003
[14]   Synthesis of functionalized polymers by means of anionic living polymerization.: 1.: Synthesis of functionalized polymers with α-methylstyryl groups by anionic reactions with use of 1-{4-[3-(4-isopropenylphenyl)propyl]phenyl}-1-phenylethylene [J].
Hirao, A ;
Haraguchi, N ;
Sugiyama, K .
MACROMOLECULES, 1999, 32 (01) :48-54
[15]  
HIRAO A, 1996, FUNCTIONAL POLYM VIA, P19
[16]  
HIRAO A, 1999, ACTA POLYM, V50
[17]  
HIRAO A, UNPUB
[18]  
Hsieh H. L., 1996, ANIONIC POLYM PRINCI, P279
[19]  
HSIEH HL, 1996, ANIONIC POLYM PRINCI, P261
[20]   SYNTHESIS AND CHARACTERIZATION OF MODEL 4-MIKTOARM STAR COPOLYMERS AND QUATERPOLYMERS [J].
IATROU, H ;
HADJICHRISTIDIS, N .
MACROMOLECULES, 1993, 26 (10) :2479-2484