Thermal degradation of poly(alkyl methacrylate) synthesized via ATRP using 2,2,2-tribromoethanol as initiator

Copper(II) Chloride/Tris(2-pyridylmethyl)amine-Catalyzed Depolymerization of Poly(n-butyl methacrylate)

“…Incubation of bromine-functionalized alkyl methacrylate oligomers, prepared by telomerization with bromotrichloromethane or tetrabromomethane, produced oligomers with lactone chain ends with the same 1780 cm –1 absorbance after incubation. − The authors noted the appearance of alkyl bromines as byproducts after incubation of methyl methacrylate telomers with bromine functionality . The same absorbance band was observed in the lactonization of PMMA–Cl and PMMA–Br after incubation in the bulk at 150 °C for half an hour. , The n -alkyl halide was detected as a volatile, and attributed to lactonization of the chain end, during the incubation of PMMA–Br prepared by ATRP using a 2,2,2-tribromoethanol initiator …”

“…The lack of mass loss at low temperature in the incubated sample suggests that the first step in the thermal decomposition of PBMA−Cl occurs predominantly at the end groups. Incubation also improved the thermal stability of bromine-functionalized poly(n-alkyl methacrylate)s. 53 The opposite observation was observed in the TGA of P(PDMSMA)−Cl, which suggests that the side chains may influence the thermal stability of polymers prepared by ATRP. 43 Loss of alkyl halide CEF was also observed in chain extension experiments of incubated macroinitiators as a decrease in initiation efficiency (Table 5).…”

“…51,52 The n-alkyl halide was detected as a volatile, and attributed to lactonization of the chain end, during the incubation of PMMA−Br prepared by ATRP using a 2,2,2-tribromoethanol initiator. 53 Decomposition of end groups was also detected by highresolution thermogravimetric analysis (HiRes-TGA) of the initial and incubated sample. HiRes-TGA of PBMA−Cl showed an additional step in thermal decomposition starting at a temperature of ∼150 °C, reaching a maximum rate of mass loss at 211 °C, before accelerated decomposition began at ∼290 °C (Figure S19).…”

Depolymerization of P(PDMS11MA) Bottlebrushes via Atom Transfer Radical Polymerization with Activator Regeneration

“…It should be noted that volatiles were not measured during TGA measurements and mass loss may be attributed to decomposition of the end groups, the methacrylate backbone, or the PDMS side chain; however, it is more likely that mass loss at low temperature closely follows decomposition of the chain end due to the high thermal stability of PDMS. , Thermal degradation of P­(PDMS 11 MA)-Cl could be compared to previous studies on halogen-capped polymethacrylates. Less mass loss was observed in TGA of bromine-capped PMMA-Br between 160 and 250 °C, relative to PMMA prepared by RP. , However, elimination and lactonization of the chain end were observed after isothermal incubation of PMMA-Br and PMMA-Cl at 150 °C by NMR and MALDI-TOF in several publications. − Incubation increased the thermal stability of bromine-capped poly­(methyl methacrylate), poly­(ethyl methacrylate), poly­( n -butyl methacrylate), and poly­( n -hexyl methacrylate) prepared by ATRP using a 2,2,2-tribromoethanol initiator . Uncatalyzed degradation of the chain end will affect the thermal stability of polymers prepared by ATRP and needs to be understood in the context of depolymerizations and applications.…”