溶液中6-O-甲基丙烯酰基-1,2; 3,4-二-O-异亚丙基-D-吡喃半乳糖的原子转移自由基聚合,Journal of Polymer Science Part A: Polymer Chemistry

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溶液中6-O-甲基丙烯酰基-1,2; 3,4-二-O-异亚丙基-D-吡喃半乳糖的原子转移自由基聚合
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 5 January 2005 , DOI: 10.1002/pola.20568
Jian-Qiang Meng , Fu-Sheng Du , Ya-Shu Liu , Zi-Chen Li

进行了载糖单体6-O-甲基丙烯酰基-1,2; 3,4-二-O-异亚丙基-D-吡喃半乳糖（MAIPGal）的原子转移自由基聚合（ATRP）的详细研究。优化与ATRP相关的因素，例如引发剂，配体，催化剂和温度，以获得对聚合的良好控制。当通过2-溴异丙酸甲酯（2-MBP），2-溴异丁酸乙酯（2-EBiB）或大分子引发剂[α-（2-溴异丁酸酯）-ω-甲基PEO]引发聚合反应时，详细研究了动力学。（PEO–Br），以联吡啶（bipy）为配体在60°C或通过2-EiBB与N，N，N '，N '' ，N室温下（23°C）以''-五甲基二亚乙基三胺（PMDETA）作为配体。还研究了催化剂（CuBr和CuCl）的作用。我们证明，对于60°C的2-EBiB / CuBr / bipy和2-MBP / CuCl / bipy和室温下的2-EBiB / CuBr / PMDETA，可以实现MAIPGal的成功ATRP。在室温下以PMDETA作为配体由2-EBiB引发应是最适中的条件并抑制许多副反应的最佳操作。通过ATRP制备的P（MAIPGal）以甲基丙烯酸甲酯（MMA）作为第二单体的扩链，得到二嵌段共聚物P（MAIPGal）-b- PMMA。功能聚合物，聚D-半乳糖6-甲基丙烯酸酯（PGMA），PEO- b -PGMA和PGMA- b除去保护基团后获得-PMMA。©2005 Wiley Periodicals，Inc. J Polym Sci A部分：Polym Chem 43：752–762，2005

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Atom transfer radical polymerization of 6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-D-galactopyranose in solution

A detailed exploration of the atom transfer radical polymerization (ATRP) of a sugar-carrying monomer, 6-O-methacryloyl-1,2;3,4-di-O-isopropylidene-D-galactopyranose (MAIPGal) was performed. The factors pertinent to ATRP, such as initiators, ligands, catalysts, and temperature were optimized to obtain good control over the polymerization. The kinetics were examined in detail when the polymerization was initiated by methyl 2-bromoisopropionate (2-MBP), ethyl 2-bromoisobutyrate (2-EBiB), or a macroinitiator, [α-(2-bromoisobutyrylate)-ω-methyl PEO] (PEO–Br), with bipyridine (bipy) as the ligand at 60 °C or by 2-EiBB with N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) as the ligand at room temperature (23 °C). The effects of the catalysts (CuBr and CuCl) were also investigated. We demonstrate that the successful ATRP of MAIPGal can be achieved for 2-EBiB/CuBr/bipy and 2-MBP/CuCl/bipy at 60 °C and for 2-EBiB/CuBr/PMDETA at room temperature. The initiation by 2-EBiB at room temperature with PMDETA as the ligand should be the most optimum operation for its moderate condition and suppression of many side reactions. Chain extension of P(MAIPGal) prepared by ATRP with methyl methacrylate (MMA) as the second monomer was carried out and a diblock copolymer, P(MAIPGal)-b-PMMA, was obtained. Functional polymers, poly(D-galactose 6-methacrylate) (PGMA), PEO-b-PGMA, and PGMA-b-PMMA were obtained after removal of the protecting groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 752–762, 2005

更新日期：2017-01-31

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