Facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer via reversible addition-fragmentation chain transfer polymerization

Zhishen Ge, Daoyong Chen, Jingyan Zhang, Jingyi Rao, Jun Yin, Di Wang, Xuejuan Wan, Wenfang Shi, Shiyong Liu

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

We report the first instance of facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer, [G-3]-PNIPAM-[G-3], consisting of third generation poly(benzyl ether) monodendrons ([G-3]) and linear poly(N-isopropylacrylamide) (PNIPAM), via reversible addition-fragmentation chain transfer (RAFT) polymerization. The key step was the preparation of novel [G-3]-based RAFT agent, [G-3]-CH2SCSSCH2-[G-3] (1), from third-generation dendritic poly(benzyl ether) bromide, [G-3]-CH2Br. Due to the bulky nature of [G-3]-CH2Br, its transformation into trithiocarbonate 1 cannot go to completion, a mixture containing ∼80 mol % of 1 and 20 mol % [G-3]-CH2Br was obtained. Dumbbell-shaped [G-3]-PNIPAM310-[G-3] triblock copolymer was then successfully obtained by the RAFT polymerization of N-isopropylacylamide (NIPAM) using 1 as the mediating agent, and trace amount of unreacted [G-3]-CH2Br was conveniently removed during purification by precipitating the polymer into diethyl ether. The dendritic-linear-dendritic triblock structure was further confirmed by aminolysis, and fully characterized by gel permeation chromatography (GPC) and 1H-NMR. The amphiphilic dumbbell-shaped triblock copolymer contains a thermoresponsive PNIPAM middle block, in aqueous solution it self-assembles into spherical nanoparticles with the core consisting of hydrophobic [G-3] dendritic block and stabilized by the PNIPAM central block, forming loops surrounding the insoluble core. The micellar properties of [G-3]-PNIPAM310-[G-3] were then fully characterized.

Original languageEnglish
Pages (from-to)1432-1445
Number of pages14
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume45
Issue number8
DOIs
Publication statusPublished - 2007 Apr 15
Externally publishedYes

Fingerprint

Block copolymers
Ethers
Polymerization
Ether
Gel permeation chromatography
Purification
Bromides
Nuclear magnetic resonance
Nanoparticles
Polymers
poly-N-isopropylacrylamide

Keywords

  • Block copolymers
  • Dendrimers
  • Reversible addition-fragmentation chain transfer (RAFT)
  • Self-assembly

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer via reversible addition-fragmentation chain transfer polymerization. / Ge, Zhishen; Chen, Daoyong; Zhang, Jingyan; Rao, Jingyi; Yin, Jun; Wang, Di; Wan, Xuejuan; Shi, Wenfang; Liu, Shiyong.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 45, No. 8, 15.04.2007, p. 1432-1445.

Research output: Contribution to journalArticle

Ge, Zhishen ; Chen, Daoyong ; Zhang, Jingyan ; Rao, Jingyi ; Yin, Jun ; Wang, Di ; Wan, Xuejuan ; Shi, Wenfang ; Liu, Shiyong. / Facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer via reversible addition-fragmentation chain transfer polymerization. In: Journal of Polymer Science, Part A: Polymer Chemistry. 2007 ; Vol. 45, No. 8. pp. 1432-1445.
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abstract = "We report the first instance of facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer, [G-3]-PNIPAM-[G-3], consisting of third generation poly(benzyl ether) monodendrons ([G-3]) and linear poly(N-isopropylacrylamide) (PNIPAM), via reversible addition-fragmentation chain transfer (RAFT) polymerization. The key step was the preparation of novel [G-3]-based RAFT agent, [G-3]-CH2SCSSCH2-[G-3] (1), from third-generation dendritic poly(benzyl ether) bromide, [G-3]-CH2Br. Due to the bulky nature of [G-3]-CH2Br, its transformation into trithiocarbonate 1 cannot go to completion, a mixture containing ∼80 mol {\%} of 1 and 20 mol {\%} [G-3]-CH2Br was obtained. Dumbbell-shaped [G-3]-PNIPAM310-[G-3] triblock copolymer was then successfully obtained by the RAFT polymerization of N-isopropylacylamide (NIPAM) using 1 as the mediating agent, and trace amount of unreacted [G-3]-CH2Br was conveniently removed during purification by precipitating the polymer into diethyl ether. The dendritic-linear-dendritic triblock structure was further confirmed by aminolysis, and fully characterized by gel permeation chromatography (GPC) and 1H-NMR. The amphiphilic dumbbell-shaped triblock copolymer contains a thermoresponsive PNIPAM middle block, in aqueous solution it self-assembles into spherical nanoparticles with the core consisting of hydrophobic [G-3] dendritic block and stabilized by the PNIPAM central block, forming loops surrounding the insoluble core. The micellar properties of [G-3]-PNIPAM310-[G-3] were then fully characterized.",
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T1 - Facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer via reversible addition-fragmentation chain transfer polymerization

AU - Ge, Zhishen

AU - Chen, Daoyong

AU - Zhang, Jingyan

AU - Rao, Jingyi

AU - Yin, Jun

AU - Wang, Di

AU - Wan, Xuejuan

AU - Shi, Wenfang

AU - Liu, Shiyong

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AB - We report the first instance of facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer, [G-3]-PNIPAM-[G-3], consisting of third generation poly(benzyl ether) monodendrons ([G-3]) and linear poly(N-isopropylacrylamide) (PNIPAM), via reversible addition-fragmentation chain transfer (RAFT) polymerization. The key step was the preparation of novel [G-3]-based RAFT agent, [G-3]-CH2SCSSCH2-[G-3] (1), from third-generation dendritic poly(benzyl ether) bromide, [G-3]-CH2Br. Due to the bulky nature of [G-3]-CH2Br, its transformation into trithiocarbonate 1 cannot go to completion, a mixture containing ∼80 mol % of 1 and 20 mol % [G-3]-CH2Br was obtained. Dumbbell-shaped [G-3]-PNIPAM310-[G-3] triblock copolymer was then successfully obtained by the RAFT polymerization of N-isopropylacylamide (NIPAM) using 1 as the mediating agent, and trace amount of unreacted [G-3]-CH2Br was conveniently removed during purification by precipitating the polymer into diethyl ether. The dendritic-linear-dendritic triblock structure was further confirmed by aminolysis, and fully characterized by gel permeation chromatography (GPC) and 1H-NMR. The amphiphilic dumbbell-shaped triblock copolymer contains a thermoresponsive PNIPAM middle block, in aqueous solution it self-assembles into spherical nanoparticles with the core consisting of hydrophobic [G-3] dendritic block and stabilized by the PNIPAM central block, forming loops surrounding the insoluble core. The micellar properties of [G-3]-PNIPAM310-[G-3] were then fully characterized.

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KW - Self-assembly

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