266953 Model-Based Monomer Feeding Strategies On Tailoring Styrene/Butyl Acrylate Copolymer with Controlled Sequence Distribution Via RAFT Miniemulsion Polymerization

Monday, October 29, 2012
Hall B (Convention Center )
Xiaohui Li1, Wen-Jun Wang1, Bo-Geng Li1 and Shiping Zhu2, (1)Department of Chemical & Biological Engineering, Zhejiang University, Hangzhou, China, (2)Department of Chemical Engineering, McMaster University, Hamilton, ON, Canada

Model-based Monomer Feeding Strategies on Tailoring Styrene/Butyl Acrylate Copolymer with Controlled Sequence Distribution via RAFT Miniemulsion Polymerization

Xiaohui Li1, Wen-Jun Wang1, Bo-Geng Li1, and Shiping Zhu2

1 State Key Laboratory of Chemical Engineering, Institute of Polymer and Polymerization Engineering, Department of Chemical & Biological Engineering , Zhejiang University, Hangzhou, Zhejiang, China 310027

2Department of Chemical Engineering, McMaster University, Hamilton, Canada L8S 4L7

Abstract Copolymer chain sequence distribution (CSD) plays an important role in tuning material properties.  The advent of controlled/living free radical polymerization (CLRP) has opened an alternative opportunity to precisely control CSD.  However, it is changeling to achieve a defined CSD control on copolymers during CLRP (mini)emulsion copolymerization.  In this work, a kinetic model for reversible addition-fragmentation chain transfer (RAFT) miniemulsion copolymerization was developed.  The model was confirmed with the experimental results of RAFT miniemulsion copolymerization of styrene (St) and butyl acrylate (BA).  The 3-benzyltrithiocarbonyl propionic acid and potassium persulfate were respectively used as a chain transfer agent and an initiator, while sodium dodecyl sulfate served as a surfactant and hexadecane performed as a costabilizer.  The conversions, molecular weights and distribution, numbers of nucleation particles, average numbers of free radical per particle, and copolymer compositions could be predicted using the model.  The model was further combined with a semi-batch reactor model.  A model-based monomer feeding strategy was thus developed to tailor St/BA copolymers with precisely designed CSD.  Series of St/BA copolymers having uniform and linear gradient structures were successfully synthesized.  The glass transition behaviors of the tailor-made St/BA copolymers were also investigated.

This work is financially supported by National Natural Science Foundation of China (Key Grant 20936006, Grant 21074116), Chinese State Key Laboratory of Chemical Engineering at Zhejiang University (Grants SKL-ChE-08D02 and SKL-ChE-12T05), and the Program for Changjiang Scholars and Innovative Research Team in University in China (IRT0942).


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