Skip to Main Content
 

Global Search Box

 
 
 
 

Files

File List


OnoI.the (final).pdf (3.46 MB)

ETD Abstract Container

Abstract Header

Optimization of the Structure of Benzocyclobutene Containing Methacrylate Monomer for Controlled Radical Polymerization

Ono, Isamu
http://rave.ohiolink.edu/etdc/view?acc_num=akron1468500945

Abstract Details

2016, Master of Science, University of Akron, Polymer Science.
Synthetic routes to benzocyclobutene (BCB)-containing methacrylate monomers were developed, and their (co) polymerization kinetics with methyl methacrylate (MMA) were investigated. Precursor 1-subsituted BCB compounds were generated via [2+2]-cycloaddition between benzyne and vinyl-substituted compounds. 1-Substituted benzocyclobutene alcohols that had 0- or 1-carbon spacers between the 1-position carbon of BCB and the hydroxyl group were subsequently synthesized through hydrolysis or reduction. Each alcohol product was esterified with methacryloyl chloride to produce a BCB-containing methacrylate monomer bearing no spacer or a one carbon spacer. The synthetic pathway to the monomer bearing a two-carbon spacer was explored and newly established. The 1-substituted BCB alcohol that had a two-carbon spacer was synthesized through a malonic ester synthesis and reduction starting from 1-bromoBCB. The alcohol product was esterified with methacryloyl chloride to yield the monomer. Each of these monomers was copolymerized with MMA by atom transfer radical polymerization (ATRP) and their kinetics was studied to investigate the controllability of the copolymerization. The copolymerizations were performed with a comonomer feed ratio (mol%) of 80/20 = MMA/BCB-monomer; there was no strong evidence of side reactions such as irreversible termination and degradative chain transfer during any of the copolymerizations. Therefore, the feed composition of BCB-monomer was increased to 50, 80, and 100 mol%. In the case of the BCB-monomer without a carbon spacer, the number average molecular weight (Mn) decrease remarkably compared to the theoretical Mn and the molecular weight dispersity (Ð) increased to around 1.40 after 12 hours-reaction with increasing BCB-monomer in the feed composition of the monomer was increased. In contrast, the other two monomers with one- or two-carbon spacer(s) were (co)polymerized in a well-controlled manner even at high BCB content in the feed. These results show that the monomers with one- or two-carbon spacer(s) enable us to synthesize BCB-containing methacrylate copolymers with well-controlled molecular weight and narrow Ð. DSC analysis was performed for the obtained copolymers (50/50). Broad exothermic peak ranging from 170 °C to 300 °C (peak maximum: around 270 °C) was observed only in the first heating scan for each copolymer, which shows BCB moieties in the copolymers underwent cross-link reaction when heated.
Coleen Pugh, Ph.D. (Advisor)
Li Jia, Ph.D. (Committee Member)
123 p.
Organic Chemistry; Polymer Chemistry; Polymers
benzocyclobutene; ATRP; atom transfer radical polymerization; methylmethacrylate; chain transfer

Recommended Citations

Citations

  • Ono, I. (2016). Optimization of the Structure of Benzocyclobutene Containing Methacrylate Monomer for Controlled Radical Polymerization [Master's thesis, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1468500945

    APA Style (7th edition)

  • Ono, Isamu. Optimization of the Structure of Benzocyclobutene Containing Methacrylate Monomer for Controlled Radical Polymerization. 2016. University of Akron, Master's thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1468500945.

    MLA Style (8th edition)

  • Ono, Isamu. "Optimization of the Structure of Benzocyclobutene Containing Methacrylate Monomer for Controlled Radical Polymerization." Master's thesis, University of Akron, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1468500945

    Chicago Manual of Style (17th edition)

akron1468500945
1,452
© 2016, all rights reserved.
This open access ETD is published by University of Akron and OhioLINK.