Synthesis, Characterization, and Photopolymerization of Polyisobutylene Phenol (Meth)acrylate Macromers

Authors

Bin Yang, University of Southern MississippiFollow
Corey M. Parada, University of Southern MississippiFollow
Robson F. Storey, University of Southern MississippiFollow

Document Type

Article

Publication Date

9-13-2016

School

Polymer Science and Engineering

Abstract

Polyisobutylene (PIB) phenol (meth)acrylates were produced by reacting di- or triphenol-terminated PIB with (meth)acryloyl chloride. ¹H NMR, GPC, and MALDI-TOF MS characterization showed that meth(acrylate) end-functionality was 2 and 3, respectively, and that targeted molecular weights and relatively low polydispersities were achieved. Comparative aliphatic PIB triol triacrylate was prepared by end-quenching living polyisobutylene with 4-phenoxy-1-butyl acrylate. A photopolymerization study of PIB diphenol di(meth)acrylates with M_n about 3000 g/mol, PIB triphenol tri(meth)acrylates with M_n about 4000 and 10 000 g/mol, and control aliphatic PIB triol triacrylate with M_n about 10 000 g/mol was conducted. Darocur 1173 and Irgacure 819 and 651 photoinitiators were studied, and FTIR reaction monitoring showed that Darocur 1173 afforded the highest rate of photopolymerization and final conversion, apparently due to its higher solubility in PIB. At M_n ≅ 4000 g/mol, the rate of photopolymerization and conversion of PIB triphenol triacrylate was faster than that of PIB triphenol methacrylate under the same conditions; at M_n ≅ 10 000 g/mol, PIB triphenol triacrylate, PIB triphenol trimethacrylate, and aliphatic PIB triacrylate all showed the same high rate of photopolymerization, which was higher than any rate observed at M_n ≅ 4000 g/mol. Similarly, PIB triphenol tri(meth)acrylate at M_n ≅ 4000 g/mol displayed a higher rate of photopolymerization and double-bond conversion than PIB diphenol di(meth)acrylate at M_n ≅ 3000 g/mol, although they have similar chain end concentrations. This phenomenon was attributed to reduced diffusional mobility at higher M_n, resulting in decreased rate of bimolecular radical termination and autoacceleration. T_g of UV-cured PIB networks decreased as M_n of PIB macromer increased regardless of end-group type, and thermal stability of cured networks remained constant regardless of end-group type. Mechanical properties were characteristic of rubbery networks, but weak, apparently due to low M_n and low PDI of the starting macromers and lack of chain entanglements. Networks from macromers with M_n ≅ 10 000 g/mol gave higher elongations, but lower Young’s moduli, compared to those from macromers with M_n ≅ 4000 g/mol.

Publication Title

Macromolecules

Volume

49

Issue

17

First Page

6173

Last Page

6185

Recommended Citation

Yang, B., Parada, C., Storey, R. (2016). Synthesis, Characterization, and Photopolymerization of Polyisobutylene Phenol (Meth)acrylate Macromers. Macromolecules, 49(17), 6173-6185.
Available at: https://aquila.usm.edu/fac_pubs/19520