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Chinese Journal of Materials Research  2014, Vol. 28 Issue (1): 8-14    DOI: 10.11901/1005.3093.2013.678
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Synthesis of Tadpole POSS Acrylate Block Copolymer as well as Preparation and Performance of Honeycomb-patterned Films from the Block Copolymer
Tao YU,Xiaoyan MA(),Yizhuo LI,Zhiguang LI,Xiu QIANG
The Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education and the Key Laboratory of Polymer Science and Technology, Shaanxi Province, School of Science, Northwestern Polytechnical University,Xi’an, 710129
Cite this article: 

Tao YU,Xiaoyan MA,Yizhuo LI,Zhiguang LI,Xiu QIANG. Synthesis of Tadpole POSS Acrylate Block Copolymer as well as Preparation and Performance of Honeycomb-patterned Films from the Block Copolymer. Chinese Journal of Materials Research, 2014, 28(1): 8-14.

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Abstract  

A honeycomblike porous film has been fabricated from a homogeneous solution of tadpole POSS acrylate block copolymer (POSS-PMMA-b-PS), which was made via atom transfer radial polymerization (ATRP) polymerization in one pot, using the static breath figures method. Taking into account of the formation mechanism of the pore, the influencing factors, such as the kind of solvent, the concentration of the solution and relative humidity for the formation of self-assembled block copolymer membrane, have been evaluated, and especially, the effects of interfaces, including air/glass wafer, air/water and air/ice interfaces, were investigated. The results show that cycloidal bubble arrays can be prepared when chloroform was chosen as solvent, concentration of POSS-PMMA-b-PS was 20 mgmL-1, relative humidity was 80%, and the solution was cast on the air/glass wafer interface; well-patterned membrane can also be prepared when the solution was cast on air/water and air/ice interfaces in the same condition; nevertheless, the pore size and hole spacing of the latter was much smaller. The result of static contact angle with water analysis shows that this porous film has good hydrophobic performance, and the contact angle increases with the decrease of pore size; the porous film shows excellent resistance to acid, alkaline and heat.

Key words:  organic polymer materials      porous membranes      breath figures      block copolymer      interfaces      hydrophobicity      heat resistance     
Received:  17 September 2013     

URL: 

https://www.cjmr.org/EN/10.11901/1005.3093.2013.678     OR     https://www.cjmr.org/EN/Y2014/V28/I1/8

Fig.1  1H NMR spectra and GPC curve of the tadpole block copolymer
Fig.2  SEM images of porous films using chloroform (a), dichloromethane (b) or tetrahydrofuran (c) as the solvent from block copolymer obtained from a polymer solution (20 mgmL-1) at an air/glass wafer interface
Fig.3  SEM images of porous films from block copolymer chloroform solution casting at air/glass wafer interface, 80% RH, with different polymer concentration (a) 5 mgml-1; (b) 10 mgml-1; (c) 15 mgml-1; (d) 20 mgml-1; (e) 30 mgml-1
Fig.4  Relative humidity dependence of the pore sizes of copolymer chloroform solution at the optimism concentration 20 mgmL-1, (a) 60% RH; (b) 70% RH; (c) 75% RH; (d) 80% RH; (e) 90% RH
RH Pore size/μm Hole spacing/μm
60% 2.05±0.19 0.39±0.14
70% 2.17±0.16 0.43±0.14
75% 2.35±0.20 0.30±0.08
80% 2.46±0.20 0.92±0.15
90% -- --
Table 1  Distribution of porous films at various relative humidity
Fig.5  SEM images of porous films from block copolymer casting at optimism condition, obtained from different two-phase interfaces, (a) air/glass wafer; (b) air/water; (c, d) air/ice
Interface Pore size/μm Hole spacing/μm
air/glass wafer 2.46±0.20 0.92±0.15
air/water 1.39±0.20 0.32±0.20
air/ice 0.85±0.21 0.54±0.15
Table 2  Distribution of porous membranes at various interfaces
Fig.6  Static contact angles and porosity measured on flat films (obtained under 15% RH via spin-coating) and on porous membranes of different pore sizes
Fig.7  Bubble arrays from copolymer before (a) and after exposing to 3 molL-1 hydrochloric acid solution (b) and sodium hydroxide solution (c) for 24 h
Fig.8  Fig.8 Bubble arrays from block copolymer after exposing to the air and heating for 1 h (a) 80℃; (b) 100℃; (c) 120℃; (d) 140℃
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