Facile Synthesis of Poly (hydroxypropylene imine) Dendrimer from a Single Monomer

Zhou Yong-cun; Zhou Zhu-xian; Shen You-qing

doi:10.11777/j.issn1000-3304.2017.16295

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Facile Synthesis of Poly (hydroxypropylene imine) Dendrimer from a Single Monomer

Research Article | 更新时间：2021-05-18

- Facile Synthesis of Poly (hydroxypropylene imine) Dendrimer from a Single Monomer
- Acta Polymerica Sinica Issue 2, Pages: 359-366(2017)
- 作者机构：
  
  浙江大学化学工程与生物工程学院杭州 310027
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.16295
  CLC：
- Published：20 February 2017，
  
  Received：21 September 2016，
  
  Revised：17 November 2016，
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Zhou Yong-cun, Zhou Zhu-xian, Shen You-qing. Facile Synthesis of Poly (hydroxypropylene imine) Dendrimer from a Single Monomer. [J]. Acta Polymerica Sinica (2):359-366(2017)
DOI：

Zhou Yong-cun, Zhou Zhu-xian, Shen You-qing. Facile Synthesis of Poly (hydroxypropylene imine) Dendrimer from a Single Monomer. [J]. Acta Polymerica Sinica (2):359-366(2017) DOI： 10.11777/j.issn1000-3304.2017.16295.

摘要

报道了一种用丙烯胺为原料合成特丁基氧甲酰基（BOC）保护的氨基环氧丙烷（BN-PO），并用它作为唯一单体、利用氨基-环氧类点击反应/BOC脱保护的连续反应，高效合成内部含有羟基、外层含氨基的聚羟基丙烯亚胺树状高分子（HOPPI）的新方法.由于利用点击反应，只需少许过量单体即可使树状高分子接枝完全且只用正己烷沉淀即可除去过量单体.用核磁氢谱表征了各代树状高分子对应的化学位移，用质谱和凝胶渗透色谱验证合成树状高分子分子量的分布.该树状高分子具有合成简单、单分散、高密度双官能团的特点，可进一步进行功能化修饰.

Abstract

Dendrimers characterized by monodisperse hyperbranched structure have been applied in many fields due to their unique properties such as precise structure

plenty of internal cavities and high density of surface functional groups. Dendrimers with internal and peripheral dual-functional groups attract much attention because of their versatility in functionalization. Herein

started from allylamine

followed by BOC protection and

-CPBA oxidation

we synthesized 3-BOC-protected

amino

-1

2-propylene oxide (BN-PO). Using BN-PO as the only monomer and by sequential amine-epoxy click reaction and BOC-deprotection

a new type of poly (hydroxypropylene imine) (HOPPI) dendrimer

with internal hydroxyl groups and peripheral amine groups

was synthesized. In the epoxy-amine click reaction

a slight excess of monomer (1.2 equiv.) was used to drive the reaction to completion

DIPEA or DABCO was used as catalyst to accelerate the reaction. A simple precipitation in hexane was sufficient to remove the unreacted monomer. HCl was used for BOC-deprotection. The resulting hydrochloride was subsequently removed using Ca (OH)

to expose free amine groups. The fourth generation dendrimer

containing 60 internal hydroxyl groups and 32 peripheral amine groups

was easily obtained using this simple and efficient synthesis procedure. The dendrimer structures were confirmed by

H-NMR spectra

mass spectra and gel permeation chromatography. The corresponding peak integral ratios in

H-NMR spectra showed proper structure of dendrimers. A side reaction in the epoxy-amine click reaction

due to the attack on different carbon

was also revealed. Mass spectra showed the mass-to-charge ratio of dendrimers

which further confirmed the precise structure of dendrimers. Gel permeation chromatography (GPC) showed a narrow distribution of the molecular weight of the dendrimers. The molecular weight obtained from GPC was smaller than the theoretical value as the hydrodynamic volume of the dendrimer was smaller than that of the linear polymers of the same molecular weight. Thus

this article provides a simple and convenient approach to synthesize monodisperse HOPPI dendrimers with high density of dual-functional groups

which are easy for various modifications in order to adopt for different applications.

关键词

树状高分子高效合成点击化学内部与表面双功能基团

Keywords

Dendrimer Facile synthesisEpoxide-amine reactionsClick reactionInternal and peripheral dual-function groups

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