Living cationic polymerization of 2‐vinyloxyethyl phthalimide: Synthesis of poly(vinyl ether) with pendant primary amino functions
Living cationic polymerization of 2‐vinyloxyethyl phthalimide: Synthesis of poly(vinyl ether) with pendant primary amino functions
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2-乙烯基氧基乙基邻苯二甲酰亚胺的活性阳离子聚合：具有侧链伯氨基官能团的聚（乙烯基醚）的合成
DOI：
10.1002/pola.1988.080261219
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发表时间：
1988
期刊：
影响因子：
--
通讯作者：
T. Higashimura
中科院分区：
文献类型：
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作者：
T. Hashimoto;H. Ibuki;M. Sawamoto;T. Higashimura
2-乙烯基氧乙基酞酰亚胺(1)在- 15℃下，以碘化氢/碘（HI/I2）为引发剂，在CH2Cl2中进行阳离子聚合，得到了分子量分布较窄（Mw/Mn = 1.1 ~ 1.25）的活性聚合物。聚合物的数均分子量与单体转化率成正比，可通过调节1/HI投料比控制在1000 ~ 6000之间。然而，当一个新的单体被提供给完全聚合的反应混合物时，聚合物的分子量并不与单体转化率成正比。三氟化硼醚（BF3OEt2）在CH2Cl2中在- 78℃下聚合得到了相对高分子量（Mw > 20,000）和宽分子量分布（Mw/Mn ~ 2）的聚合物。HI/ i2引发的1的聚合比乙基乙烯醚的聚合慢一个数量级，可能是由于吸电子的邻苯二胺悬垂。酰亚胺在聚(1)中的功能水解得到具有脂肪族伯胺悬垂物的水溶性聚（乙烯醚）(3)。
Cationic polymerization of 2-vinyloxyethyl phthalimide (1) in CH2Cl2 at −15°C with hydrogen iodide/iodine (HI/I2) as initiator led to living polymers of a narrow molecular weight distribution (Mw/Mn = 1.1–1.25). The number-average molecular weight of the polymers was in direct proportion to monomer conversion and could be controlled in the range of 1000–6000 by regulating the 1/HI feed ratio. However, when a fresh monomer was supplied to the completely polymerized reaction mixture, the molecular weight of the polymers was not directly proportional to monomer conversion. The polymerization of 1 by boron trifluoride etherate (BF3OEt2) in CH2Cl2 at −78°C gave polymers with relatively high molecular weight (Mw > 20,000) and broad molecular weight distribution (Mw/Mn ∼ 2). The HI/I2-initiated polymerization of 1 was an order of magnitude slower than that of ethyl vinyl ether, probably because of the electron-withdrawing phthalimide pendant. Hydrazinolysis of the imide functions in poly(1) gave a water-soluble poly(vinyl ether) (3) with aliphatic primary amino pendants.