Citation: Yi-wei Liang, Peng Liu, Shu-xing Yin, Jing-rui Liu, Ming-zu Zhang, Jin-lin He, Pei-hong Ni. Preparation and Characterization of Functionalized POSS Derivatives and Multi-arm Star-shaped Polyesters[J]. Acta Polymerica Sinica, ;2020, 51(4): 366-376. doi: 10.11777/j.issn1000-3304.2019.19210 shu

Preparation and Characterization of Functionalized POSS Derivatives and Multi-arm Star-shaped Polyesters

College of Chemistry, Chemical Engineering and Materials Science, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Soochow University, Suzhou 215123

Corresponding author: Jin-lin He, jlhe@suda.edu.cn
Received Date: 16 December 2019
Revised Date: 9 January 2020
Available Online: 12 March 2020

Figures(10)

A set of functional POSS derivatives and star-shaped POSS-cored polyesters are presented. Three POSS derivatives POSS-8OH, POSS-16OH and POSS-8NH₂are prepared by thiol-ene “click” reaction of octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) with 2-mercapto-ethanol, 1-thioglycerol and cysteamine hydrochloride. Their chemical structures are confirmed by ¹H-NMR, ¹³C-NMR, and FTIR analyses. Subsequently, POSS-8OH and POSS-16OH are used to initiate the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and 2-ethoxy-2-oxo-1,3,2-dioxaphospholane (EOP), resulting in hydrophobic 8-arm (POSS-8PCL) and 16-arm (POSS-16PCL) star-shaped poly(ε-caprolactone), as well as hydrophilic 8-arm star-shaped poly(ethyl ethylene phosphate) (POSS-8PEEP). Three star-shaped POSS-8PCL with different arm lengths are synthesized by changing the feed ratio of the monomer to initiator. As a demonstration, the chemical structure of POSS-8PCL-2 is confirmed by using FTIR, ¹H-NMR and ¹³C-NMR analyses. TGA test indicates that the initial decomposition temperature and decomposition mode are influenced by the molecular weights of POSS-8PCL. In order to compare the thermal stability of star-shaped PCL with a POSS core or an organic core, tripentaerythritol (TPE) is used to initiate the ROP reaction of ε-CL to give eight-arm PCL (TPE-8PCL) with an organic core. TGA test demonstrates that inorganic POSS core has better support to maintain melt stability of 8-arm star-shaped PCL than organic TPE core. The chemical structure and molecular weight information of POSS-16PCL are characterized by FTIR, ¹H-NMR and ¹³C-NMR analyses, as well as GPC test. TGA analysis shows that the initial decomposition temperature is around 200 °C, the decomposition behavior also displays an apparent two-stage mode, and the residue derived from POSS segment is about 3.6% at 700 °C. Finally, POSS-8OH is used to initiate the ROP reaction of EOP to obtain POSS-8PEEP. The chemical structure and molecular weight information of POSS-8PEEP are confirmed by FTIR, ¹H-NMR and GPC analyses. Furthermore, TGA analysis demonstrates that the thermal stability of POSS-8PEEP is weaker than star-shaped PCL and the initial decomposition temperature is decreased to about 100 °C. The decomposition of POSS-8PEEP shows a more apparent multi-stage mode and about 19.8% residue is left at 700 °C. This work reports a facile method for the preparation of functional POSS derivatives and star-shaped POSS-cored polymers.
- Star-shaped polymer,
- Poly(ε-caprolactone),
- Polyphosphoesters,
- Thiol-ene “click” reaction,
- Polyhedral oligomeric silsesquioxane
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