Synthesis of Poly(Methyl Methacrylate)-Based Polyrotaxane via Reversible Addition-Fragmentation Chain Transfer Polymerization.

A polyrotaxane (PR) with poly(methyl methacrylate) (PMMA) as the main chain polymer was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Because of the special mechanism of RAFT, the suprastructure of a PMMA-based PR is established by synthesizing inclusion complexes of methyl methacrylate and gamma-cyclodextrin (γCD) into the middle of the poly-N-(3-dimethylamino) propyl methacrylamide segments. The presence of threaded γCD was determined via diffusion ordered spectroscopy from the alignment of the mobility of γCD and the main chain polymer. A PMMA-based PR with 2-20% CD coverage and a molecular weight of 7K-60K g/mol of PMMA-based PR was synthesized with a targeted molecular structure by mediating the RAFT polymerization. The PMMA-based PR prepared in this study is expected to be suitable for wide applications of tough materials with good heat resistance. Moreover, the investigation of this synthetical approach opened possibilities for more variety of PR with controllable properties.

[1]  L. Ye,et al.  Synthesis and Characterization of Polyrotaxanes Comprising γ‐CDs and Distal Azide‐Terminated PHEMA Using Propargylamine Monosubstituted β‐CDs as End Stoppers , 2020 .

[2]  Kazuaki Kato,et al.  Highly Stretchable and Instantly Recoverable Slide-Ring Gels Consisting of Enzymatically Synthesized Polyrotaxane with Low Host Coverage , 2018, Chemistry of Materials.

[3]  Kazuaki Kato,et al.  Unusual Fracture Behavior of Slide-Ring Gels with Movable Cross-Links. , 2017, ACS macro letters.

[4]  Sébastien Perrier,et al.  50th Anniversary Perspective: RAFT Polymerization—A User Guide , 2017 .

[5]  T. Uyar,et al.  Selective and Efficient Removal of Volatile Organic Compounds by Channel-type Gamma-Cyclodextrin Assembly through Inclusion Complexation , 2017 .

[6]  G. Wenz,et al.  Rotaxanation of Polyisoprene to Render it Soluble in Water , 2017 .

[7]  L. Ye,et al.  Self-assemblies of γ-CDs with pentablock copolymers PMA-PPO-PEO-PPO-PMA and endcapping via atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine , 2015, Beilstein journal of organic chemistry.

[8]  N. Buang,et al.  A Review of the Properties and Applications of Poly (Methyl Methacrylate) (PMMA) , 2015 .

[9]  V. N. Paunov,et al.  Cyclodextrin stabilised emulsions and cyclodextrinosomes. , 2013, Physical chemistry chemical physics : PCCP.

[10]  Zheng Dang,et al.  A Comparative Study on the Formation and Spectral Properties of the Polypseudorotaxanes of β-Cyclodextrin and Poly(propylene glycol) under Different Conditions , 2009 .

[11]  M. Akashi,et al.  Formation of Inclusion Complexes of Isotactic and Syndiotactic Poly(methyl methacrylate)s with γ-Cyclodextrin , 2008 .

[12]  Bao-hang Han,et al.  Cyclodextrin rotaxanes and polyrotaxanes. , 2006, Chemical reviews.

[13]  A. Harada,et al.  Complex formation between polyisobutylene and cyclodextrins: inversion of chain-length selectivity between .beta.-cyclodextrin and .gamma.-cyclodextrin , 1993 .

[14]  Takashi Kashiwagi,et al.  Thermal and oxidative degradation of poly(methyl methacrylate): weight loss , 1985 .