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Controlled polymerization of 2-(diethylamino)ethyl methacrylate and its block copolymer with N-isopropylacrylamide by RAFT polymerization

Authors

  • Li Liu,

    Corresponding author
    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
    • Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Chenglin Wu,

    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Jiechun Zhang,

    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Mingming Zhang,

    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Yuwei Liu,

    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Xiaojuan Wang,

    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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  • Guoqi Fu

    1. Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
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Abstract

Poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) homopolymers with low polydispersities were synthesized by reversible addition fragmentation chain transfer (RAFT) radical polymerization. The performances of two chain transfer agents, 2-cyanoprop-2-yl dithiobenzoate and 4-cyanopentanic acid dithiobenzoate (CPADB), were compared. It was found that the polymerization of 2-(diethylamino) ethyl methylacrylate was under good control in the presence of CPADB with 4,4′-azobis(4-cyanopentanoic acid) (ACPA) as initiator in 1,4-dioxane at 70 °C. The kinetic behaviors were investigated under different CPADB/ACPA molar ratios. A long polymerization inhibition period was observed at high [CPADB]/[ACPA] ratio. The influences of [CPADB]/[ACPA] ratio, monomer/[CPADB] ratio, and temperature were studied with respect to monomer conversion, molecular weight control, and polydispersity index (PDI). The PDI decreased from 1.21 to 1.12, as the CPADB/ACPA molar ratio changed from 2 to 10. The molecular weight of PDEAEMA could be controlled by monomer/CPADB molar ratio. The control over MW and PDI was improved as the temperature increased from 60 to 70 °C; however, an additional increase to 80 °C led to a loss of control. Using PDEAEMA macroRAFT agent, pH/thermo double-responsive block copolymers of PDEAEMA and poly(N-isopropylacrylamide) (PDEAEMA-b-PNIPAM) with narrow polydispersity (PDI, 1.24) were synthesized. The lower critical solution temperature of PDEAEMA-b-PNIPAM block copolymer depended on the environmental pH. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3294–3305, 2008

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