Citation: Qi-quan Ye, Ming-xin Zheng, Xi Chen, Dan Li, Wei-guo Tian, Jun Zhang, Jin-ying Yuan. Photo-responsive Spiropyrane-containing Block Copolymer Assemblies Prepared by Polymerization-induced Self-assembly[J]. Acta Polymerica Sinica, ;2019, 50(4): 344-351. doi: 10.11777/j.issn1000-3304.2018.18256 shu

Photo-responsive Spiropyrane-containing Block Copolymer Assemblies Prepared by Polymerization-induced Self-assembly

1.
Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084
2.
Beijing National Labotatory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemsitry, Chinese Academy of Sciences, Beijing 100190

Corresponding author: Jin-ying Yuan, yuanjy@mail.tsinghua.edu.cn
Received Date: 27 November 2018
Revised Date: 16 January 2019
Available Online: 25 February 2019

A series of spiropyrane-containing copolymer assemblies— poly(N,N-dimethylaminoethyl methacrylate)-b-poly{(benzyl methacrylate)-co-[1'-(2-methacryloxyethyl)-3',3'-dimethyl-6-nitro-spiro(2H-1-benzo-pyran-2,2'-indoline)]} (PDMA-b-P(BzMA-co-SPMA)) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA), where SPMA units act as the photo-responsive moieties, P(BzMA-co-SPMA) chains as the core-forming blocks, and PDMA chains as shell-forming blocks. First, PDMA was prepared by RAFT polymerization in ethanol at 80 °C. With PDMA as macro chain transfer agent, the RAFT PISA of BzMA and SPMA in ethanol at 70 °C were completed. By changing the feed ratios of BzMA, SPMA, and PDMA, diverse morphologies, such as spheres, worms, " octopus”-like structures, vesicles, and solid particles, were readily prepared. During UV irradiation, the absorbance maximum at 585 nm increased successively, suggesting the spiropyrane structure gradually isomerized into merocyanine structure. As a result, copolymer assembly dispersion underwent a colorless-to-colorful transformation. Subsequently, the colorful copolymer assembly dispersion was exposed to visible light. The results suggested that the absorbance maximum at 585 nm gradually decreased and the colorful copolymer assembly dispersion transformed into colorless. Using the copolymer assembly dispersion as ink, the characters and patterns were drawn on papers. Since the copolymer assembly dispersion was colorless, the characters and patterns were invisible. Upon UV irradiation, with spiropyrane isomerized into merocyanine, the characters and patterns changed to blue and visible, while upon visible light irradiation or heating, merocyanine structure isomerized into spiropyrane, which induced the characters and patterns to become colorless and invisible. Taking advantage of ink-jet printing, fine-patterned patterns and two-dimensional materials could be rapidly and massively produced, which also underwent reversible invisible-to-visible transformation, upon alternative UV irradiation and visible light irradiation/heating.
- Polymerization-induced self-assembly,
- Spiropyrane,
- Photo-responsive coloration,
- Ink-jet printing,
- Stimuli-response
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