Synthesis of hyperbranched carbohydrate polymer by ring-opening multibranching polymerization of 1,4-anhydroerythritol and 1,4-anhydro-L-threitol
Synthesis of hyperbranched carbohydrate polymer by ring-opening multibranching polymerization of 1,4-anhydroerythritol and 1,4-anhydro-L-threitol
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DOI：
10.1021/ma0358024
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发表时间：
2004-05-04
期刊：
影响因子：
5.5
通讯作者：
Kakuchi, T
中科院分区：
文献类型：
--
作者：
Imai, T;Satoh, T;Kakuchi, T
以三氟甲磺酸（CF_3SO_3H）或氟磺酸（FSO_3H）为阳离子引发剂，对1，4-脱水山梨醇（1a）和1，4-脱水-L-苏糖醇（1b）进行聚合。1a和1b的聚合通过具有质子转移反应的开环反应进行，以分别产生主要由β-和L-苏糖醇单元组成的超支化碳水化合物聚合物（2a和2b）。通过2a和2b的C-13 NMR谱估计的支化度（DB）为约1.5。0.28-0.47.使用所得超支化碳水化合物聚合物的静态激光散射（SLS）估计的重均分子量（M-w，（SLS））值（3.2 × 10（4）-5.1 × 10（5））显著高于使用尺寸排阻色谱法（SEC）估计的重均分子量（M-w，SEC）值（1.5 × 10（3）-1.4 × 10（4））。2a和2b的溶液粘度非常低，并且2a和2b的特性粘度（[eta]）在3.26 × 10（-2）至7.30 × 10（-2）dL.g（-1）的范围内。通过SLS和粘度测量表征的三维性质表明，2a和2b应该是纳米颗粒。
1,4-Anhydroerythritol (1a) and 1,4-anhydro-L-threitol (1b) were polymerized using trifluoromethanesulfonic acid (CF3SO3H) or fluorosulfonic acid (FSO3H) as a cationic initiator. The polymerizations of la and 1b, proceeded through a ring-opening reaction with a proton-transfer reaction to produce hyperbranched carbohydrate polymers (2a and 2b) mainly consisting of erythritol and L-threitol units, respectively. The degrees of branching (DB) estimated by the C-13 NMR spectra of 2a and 2b were ca. 0.28-0.47. The weight-average molecular weight (M-w,(SLS)) values (3.2 X 10(4) - 5.1 x 10(5)) estimated using static laser light scattering (SLS) of the resulting hyperbranched carbohydrate polymers were significantly higher than the weight-average molecular weight (M,SEC) values (1.5 x 10(3)-1.4 x 10(4)) estimated using size exclusion chromatography (SEC). The solution viscosities of 2a and 2b were very low, and the intrinsic viscosities ([eta]) of 2a and 2b were in the range from 3.26 x 10(-2) to 7.30 x 10(-2) dL.g(-1). The three-dimensional properties characterized by the SLS and viscosity measurements indicated that 2a and 2b should be nanoscale particles.