Synthesis of high glass transition temperature (meth)acrylic polymers bearing norbornadiene dimer via Lewis pair polymerization
Year: 2025
Type: article
Abstract: The introduction of bulky and rigid polycyclic hydrocarbons into the polymer side chains increased the glass transition temperature ( T g ), thereby broadening the application range of the polymer. We synthesized and polymerized new acrylate and methacrylate monomers bearing a norbornadiene dimer, exo-exo -4-pentacyclo[8.2.1.1 5,8 .0 2,9 .0 3,7 ]tetradecanyl acrylate ( 1 ) and its methacrylate analog ( 2 ). The polymerizations of 1 and 2 using Lewis pair catalysts comprising B(C 6 F 5 ) 3 /PPh 3 and methylaluminum bis(2,6-di- tert -butyl-4-methylphenoxide) (MAD)/PCy 3 , respectively, proceeded with full conversion. The T g values of poly 1 and poly 2 were approximately 120 °C and 200 °C, respectively. Considering the T g and tacticity of poly 2 obtained via radical polymerization ( T g = 135 °C; rr triad = 63%), the significantly higher T g value ( T g = 206 °C) can be reasonably assumed to be due to the high syndiotacticity ( rr = 87%), which is likely induced by the steric repulsion between the bulky MAD at the propagating terminal and the penultimate norbornadiene dimer moiety.
Source: Polymer Journal
Authors: Miona Iwai, Shin-ichi Matsuoka
Institution: Nagoya Institute of Technology
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,390
Award: G4248525099
OpenAlex ID: W4413805003