Synthesis of new amphiphilic diblock copolymers and their self-assembly in aqueous solution

被引:83
作者
Garnier, S
Laschewsky, A
机构
[1] Univ Potsdam, D-14415 Potsdam, Germany
[2] Fraunhofer Inst Appl Polymer Res, FhG IAP, D-14476 Potsdam, Golm, Germany
关键词
D O I
10.1021/ma0506785
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Amphiphilic diblock copolymers composed of poly(butyl acrylate) as the hydrophobic block with a low glass transition temperature and of six different hydrophilic blocks (one anionic, one cationic, and four nonionic hydrophilic blocks) are prepared via reversible addition fragmentation chain transfer (RAFT) polymerization. The nonionic hydrophilic blocks comprise in addition to the classical poly(dimethylacrylamide), the thermally sensitive poly(N-acryloylpyrrolidine), and a comb-type polymer made of a poly(ethylene glycol acrylate) macromonomer, as well as a new strongly hydrophilic sulfoxide polymer. The "living" character of the polymerizations is supported by very low polydispersity indexes and a good correlation between the molar masses obtained and the theoretically expected ones. Two distinct glass transition temperatures were found by differential scanning calorimetry for the block copolymers, suggesting the immiscibility of the blocks in bulk. The self-assembling properties of the amphiphilic diblock copolymers in aqueous and organic media were studied by nuclear magnetic resonance spectroscopy and dynamic light scattering, as a function of the polarity of the hydrophilic blocks, the ratio of the lengths of the two blocks, and the overall molar mass of the diblock copolymers. Micellelike aggregates with diameters from 25 to 100 mn in water are found, as well as inverse micelles in organic solvents. The length of the hydrophobic block seems to be the main factor governing the size of the aggregates in water. The aggregates are very stable upon dilution and temperature cycles. For large hydrophobic blocks, big structures are observed in addition to small micelles initially after the dispersion in water. As the big aggregates disappear slowly, the micellization process seems thermodynamically favored. If two populations of micelles made from different block copolymers are brought together, "mixed" micelles are formed. The implicit exchange of polymers proves the dynamic character of the micellar systems based on poly(butyl acrylate) as hydrophobic block.
引用
收藏
页码:7580 / 7592
页数:13
相关论文
共 99 条
[91]   Stimulus-responsive water-soluble polymers based on 2-hydroxyethyl methacrylate [J].
Weaver, JVM ;
Bannister, I ;
Robinson, KL ;
Bories-Azeau, X ;
Armes, SP ;
Smallridge, M ;
McKenna, P .
MACROMOLECULES, 2004, 37 (07) :2395-2403
[92]   Molecular exchange in PEO-PB micelles in water [J].
Won, YY ;
Davis, HT ;
Bates, FS .
MACROMOLECULES, 2003, 36 (03) :953-955
[93]   A novel approach to biodegradable block copolymers of ε-caprolactone and δ-valerolactone catalyzed by new aluminum metal complexes [J].
Yang, J ;
Jia, L ;
Yin, LZ ;
Yu, JY ;
Shi, Z ;
Fang, Q ;
Cao, AM .
MACROMOLECULAR BIOSCIENCE, 2004, 4 (12) :1092-1104
[94]   Self-assembling of biocompatible BAB amphiphilic triblock copolymers PLL(Z)-PEG-PLL(Z) in aqueous medium [J].
Yang, ZG ;
Yuan, JJ ;
Cheng, SY .
EUROPEAN POLYMER JOURNAL, 2005, 41 (02) :267-274
[95]   Heat-induced association and dissociation behavior of amphiphilic diblock copolymers synthesized via reversible addition-fragmentation chain transfer radical polymerization [J].
Yusa, S ;
Shimada, Y ;
Mitsukami, Y ;
Yamamoto, T ;
Morishima, Y .
MACROMOLECULES, 2004, 37 (20) :7507-7513
[96]   Synthesis of well-defined amphiphilic block copolymers having phospholipid polymer sequences as a novel blocompatible polymer micelle reagent [J].
Yusa, SI ;
Fukuda, K ;
Yamamoto, T ;
Ishihara, K ;
Morishima, Y .
BIOMACROMOLECULES, 2005, 6 (02) :663-670
[97]   A convenient method of tuning amphiphilic block copolymer micellar morphology [J].
Zhang, WQ ;
Shi, LQ ;
An, YL ;
Gao, LC ;
Wu, K ;
Ma, RJ .
MACROMOLECULES, 2004, 37 (07) :2551-2555
[98]   Directly resolved core-corona structure of block copolymer micelles by cryo-transmission electron microscopy [J].
Zheng, Y ;
Won, YY ;
Bates, FS ;
Davis, HT ;
Scriven, LE ;
Talmon, Y .
JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (47) :10331-10334
[99]   Reversible addition-fragmentation chain transfer polymerization of glycidyl methacrylate with 2-cyanoprop-2-yl 1-dithionaphthalate as a chain-transfer agent [J].
Zhu, J ;
Zhou, D ;
Zhu, XL ;
Chen, GJ .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2004, 42 (10) :2558-2565