2014 AIChE Annual Meeting, Paper ID: 364354

The Triplet “Structure-Property-Synthesis Methodology” Multi-Scale Study based on Stimuli-Responsive Brush Copolymers Jin-Jin Li, Zheng-Hong Luo*

Department of Chemical Engineering, School of Chemistry and Chemical Engineering, Shanghai

Jiao Tong University, Shanghai 200240, P. R. China

* Correspondence to: Professor Z.H. Luo; e-mail: luozh@sjtu.edu.cn

Abstract:

Stimuli-responsive copolymers have aroused great interest over the past several decades, however their applied research is currently very little.1 Facing challenges from dynamic and demanding markets, the ongoing paradigm of chemical engineering begins to shift from process design to product design.2, 3
In this work, the relationship between synthesis methodology and molecular structure was established through the preparation of random, diblock and gradient linear backbone copolymers [poly(methyl methacrylate-co-2-(2-bromoisobutyryloxy) ethyl methacrylate, P(MMA-co-BIEM)] based on batch atom transfer radical polymerization (ATRP), sequential batch ATRP, and model based semi-batch ATRP, respectively.4,5
Subsequently, pH-responsive brush copolymers [i.e. P(MMA-co-BIEM)-graft-acrylic acid (AA)] with random, gradient and block backbone composition profiles were prepared via graft-from method. The tunable pH-responsive self-assembly and Ca2+ responsive behaviors of brush copolymers were achieved by controlling the composition profile of backbone.6 Considering the complexation between metal ions and polyelectrolyte chains, the as-prepared polymers have a promising perspective in water treatment system.7
Compared with the pH value and the salt concentration, temperature is a stimulus which can be uniformly adjusted. Poly(N-isopropylacrylamide) (PNIPAM) with an easily accessible lower critical solution temperature (LCST~32 °C) in water8 was introduced to the different backbone structure as mentioned above. Their structure

2014 AIChE Annual Meeting, Paper ID: 364354

depended temperature-responsive micelle in aqueous medium and thermal responsive wettability behaviors were also system investigated. The results show that the polymers modified surfaces have reversibly switchable wettability and excellent stability.
Based on the completed triplet “structure-property-synthesis methodology” multi-scale correlation, chemical product engineering perspective was introduced to develop the as-prepared Ca2+-responsive and temperature-responsive brush copolymers into new chemical products, which can be used as water treatment agent and thermal responsive coating. The whole study can be seen as case studies of manufacturing a useful product with desired function from individual molecules based on chemical polymerization method and chemical product engineering perspective.
The theme of this work was illustrated in Scheme 1.

Scheme 1. Relationship between chemistry and chemical product engineering

Keywords: Chemical product engineering, Ca2+/temperature-responsive brush copolymer, Water treatment agent, Thermal responsive wettability

References:

1 Guo, X. D.; Zhang, L. J.; Chen, Y.; Qian, Y. Core/shell pH-sensitive micelles self-assembled from cholesterol conjugated oligopeptides for anticancer drug

2014 AIChE Annual Meeting, Paper ID: 364354

delivery. AIChE J. 2010, 56, 1922.
2 Costa, R.; Moggridge, G. D.; Saraiva, P. M. Chemical product engineering: an emerging paradigm within chemical engineering. AIChE J. 2006, 52, 1976.
3 Cussler, E. L.; Wei, J. Chemical product engineering. AIChE J. 2003, 49, 1072.
4 Zhou, Y. N.; Li, J. J.; Luo, Z. H. Synthesis of gradient copolymers with simultaneously tailor-made chain composition distribution and glass transition temperature by semibatch ATRP: from modeling to application. J Polym Sci, Part A: Polym Chem. 2012, 50, 3052.
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