Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature†

doi:10.7503/cjcu20170546

Abstract

Abstract:

The implementation of photoinitiators and photocatalysts-free visible light induced reversible addition-fragmentation chain transfer(RAFT) polymerization processes at room temperature has the potential to afford greener methodology to the preparation of polymeric materials. However, these previous works pointed out that photoinduced RAFT polymerization of styrene(St) at room temperature was very slowly even with exogenous photoinitiators or photocatalysts. In this work, we aim to overcome these drawbacks via the implementation of commercial blue light-emitting diodes(LEDs) as visible light source in the RAFT polymerization of St at room temperature with S-1-dodecyl-S'-(α,α'-dimethyl-α″-aceticacid)trithiocarbonate(DDMAT) as RAFT agent, without exogenous photoinitiators or photocatalysts. The polymerization rate was comparatively rapid and the results of polymerization kinetics of St show that the polymerization exhibits good living characteristics. Importantly, the polymerization could be instantly switch “On” or “Off ” in response to visible light, and the switching cycles of light had no effect on the living character of polymerization. Finally, the photo-fragmentation and photo-degradation of DDMAT were investigated by in situ ¹H NMR(nuclear magnetic resonance) spectroscopy. The detailed study provides a deeper understanding of the chemical processes of the polymerization method.

Key words: Reversible addition-fragmentation chain transfer(RAFT) polymerization, Styrene(St), Blue light-emitting diode(LED), Kinetics property

CLC Number:

O631

TrendMD:

LUO Juxiang, CHENG Deshu, LI Mingchun, XIN Meihua. Visible Light Induced Rapid Reversible Addition-fragmentation Chain Transfer Polymerization(RAFT )of Styrene at Room Temperature^†[J]. Chem. J. Chinese Universities, 2018, 39(4): 800.

Figures/Tables 13

Scheme 1 Schematic of the visible light induced RAFT polymerization of St at room temperature

Fig.1 Absorption spectra of 0.1 mmol/L(A) and 5.0 mmol/L(B) DDMAT in ethanol

Fig.2 GPC trace of polystyrene(PSt) synthesized via visible light induced RAFT polymerization[St]0:[DDMAT]0=100:1, [M]0=48 mmol.

Fig.3 ln([M]0/[M]) as a function of time for the visible light induced RAFT polymerization of St

Fig.4 Mn and Mw/Mn versus conversion for visible light induced RAFT of St

Fig.5 GPC traces of PSt synthesized via RAFT polymerization

Fig.6 GPC traces for PSt-b-PBA(a) and PSt-TTC(b)

Fig.7 1H NMR spectrum of PSt-TTC

Fig.8 1H NMR spectrum of PSt-b-PBA polymer

Fig.9 Conversion as a function of time in “On/Off” experiment of visible light induced RAFT polymerization

Fig.10 Mn and Mw/Mn as a function of conversion in “On/Off” experiment of visible light induced RAFT polymerization

Fig.11 1H NMR spectra of 10 mmol/L(A) and 50 mmol/L(B) DDMAT solution before(a) and after the light radiation[30 min(b) and 60 min(c)]

Fig.12 1H NMR spectra of 50 mmol/L DDMAT solution before(a) and after(b) the light radiation

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