Citation: Lue Xiang, Wen Zhu, Mei-lin Long, Ke Zhang, Yong-ming Chen. Synthesis of Triblock Bottlebrush Copolymer and Its Solution Self-assembly to Form Porous Nanoparticles[J]. Acta Polymerica Sinica, ;2018, 0(7): 917-929. doi: 10.11777/j.issn1000-3304.2018.18043 shu

Synthesis of Triblock Bottlebrush Copolymer and Its Solution Self-assembly to Form Porous Nanoparticles

Lue Xiang ^1,3 ,
Wen Zhu ¹ ,
Mei-lin Long ¹ ,
Ke Zhang ^1,3,, ,
Yong-ming Chen ^2,,

1.
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
2.
School of Materials Science and Engineering, Sun Yat-Sen University, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Guangzhou 510275
3.
School of Chemical Science, University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Ke Zhang, kzhang@iccas.ac.cn Yong-ming Chen, chenym35@mail.sysu.edu.cn
Received Date: 5 February 2017
Revised Date: 9 March 2017
Available Online: 7 May 2018

A triblock bottlebrush copolymer, poly(N,N-dimethyl acrylamide)-block-(polyacrylate-graft- (polystyrene-alternate-poly(L-lactide)))-block-poly(N,N-dimethyl acrylamide) (PDMA-b-(PA-g-(PS-alt-PLLA))-b-PDMA), was prepared with an amphiphilic coil-rod-coil macromolecular structure based on the combination of reversible addition-fragmentation chain transfer polymerization (RAFT), copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC), and ring-opening polymerization (ROP). For the formation of the triblock bottlebrush copolymer, RAFT was used to prepare the well-defined triblock copolymer main chain of PDMA-b-PA-b-PDMA. CuAAC was then employed to graft the PS side chains onto the reactive PA block to form the triblock bottlebrush copolymer PDMA-b-(PA-g-PS)-b-PDMA with PS side chains. The in situ ROP of L-lactide to graft PLLA from PA block finally produced the triblock bottlebrush copolymer of PDMA-b-(PA-g-(PS-alt-PLLA))-b-PDMA with V-shaped side chains of PS and PLLA. In this macromolecule, PDMA formed the hydrophilic coil blocks while the bottlebrush polymer of PA-g-(PS-alt-PLLA) formed the hydrophobic rod block. Self-assembly of the amphiphilic PDMA-b-(PA-g-(PS-alt-PLLA))-b-PDMA was subsequently investigated in selective solvents. Due to the unique coil-rod-coil molecular structure, this triblock bottlebrush copolymer self-assembled into sheet-like micelles or vesicles in the selective solvents of THF/methanol or THF/ethanol, respectively. In these self-assemblies, the coil hydrophilic PDMA block formed the dispersing shell to keep their dispersion while the rigid hydrophobic bottlebrush block aggregated into the sheet-like cores to maintain stability of the self-assemblies. The PS and PLLA side chains with V-shaped structure along the middle blocks microphase-separated inside the aggregated micellar sheet or vesicle wall, in which the isolated PLLA microdomain was surrounded by the continuous PS microdomain. Furthermore, the selective hydrolysis of PLLA microdomain left the nanopores inside the cores of micelles and vesicles. It has been demonstrated the hydrolysis rate was heavily depended on the morphology of the self-assemblies, where the hydrolysis of PLLA microdomains of sheet-like micelles was much faster than that of the corresponding vesicles.
- Bottlebrush copolymer,
- Block copolymer,
- Microphase separation,
- Porous nanoparticles,
- Solution self-assembly
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis of Triblock Bottlebrush Copolymer and Its Solution Self-assembly to Form Porous Nanoparticles

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com