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Synthesis of High Molecular Weight Poly (methyl methacrylate) by ARGET ATRP

Qiu, Jialin
http://orcid.org/0000-0002-5142-1599
http://rave.ohiolink.edu/etdc/view?acc_num=akron1436527275

Abstract Details

2015, Master of Science in Polymer Engineering, University of Akron, Polymer Engineering.
Synthesis of poly (methyl methacrylate) by activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) was extensively studied. It was observed that when the target molecular weight is higher, side reactions and terminations becomes more prominent. In this study, a facile method was used to synthesize high molecular weight PMMA by ARGET ATRP. The effect of solvent, catalyst and ligand were discussed systematically. Low molecular weight polyethylene glycol (PEG) (600 g/mol) as solvent significantly increased the reaction rate and provides molecular weight as high as 96 kDa within 2h reaction, Ð as low as 1.2. PEG can stabilize the catalyst by complexing to avoid the side reactions such as the reactions between catalyst and chain end. The terminal hydroxyl group could potentially increase the reaction rate. It was also observed that the results have PEG molecular weight dependence. As PEG molecular weight increased, viscosity increased which resulted in poor polymer chain diffusion. However PEG-metal stability constant increased when PEG molecular weight increased which provided better control. These factors competitively affected the polymerization kinetics. Optimum solvent was observed using PEG (600 Da). The comparison between two copper based catalysts CuBr2 and CuCl2 showed that shorter bond length of Cu-Br leaded to a faster reaction rate. For the comparison of ligands, N,N,N',N',N''-pentamethyldiethylenetriamine (PMDETA) as a tridentate ligand had weaker reducing ability but stronger coordination ability compared to tetramethylethylenediamine (TMEDA) as bidentate ligand. Synthesized PMMA was used as macroinitiator to synthesize poly (methyl methacrylate)-block-polystyrene (PMMA-PS) block copolymer by bulk ARGET ATRP. With the increasing amount of styrene, PMMA diffusion became better and prematurely termination was reduced. PMMA-PS with molecular weight of 770 kDa and Ð of 1.32 was successfully synthesized.
Kevin Cavicchi (Advisor)
Bryan Vogt (Advisor)
Alamgir Karim (Committee Member)
Sadhan Jana (Committee Chair)
84 p.
Polymer Chemistry; Polymers
PMMA; ARGET ATRP; high molecular weight

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Citations

  • Qiu, J. (2015). Synthesis of High Molecular Weight Poly (methyl methacrylate) by ARGET ATRP [Master's thesis, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1436527275

    APA Style (7th edition)

  • Qiu, Jialin. Synthesis of High Molecular Weight Poly (methyl methacrylate) by ARGET ATRP. 2015. University of Akron, Master's thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1436527275.

    MLA Style (8th edition)

  • Qiu, Jialin. "Synthesis of High Molecular Weight Poly (methyl methacrylate) by ARGET ATRP." Master's thesis, University of Akron, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1436527275

    Chicago Manual of Style (17th edition)

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This open access ETD is published by University of Akron and OhioLINK.
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