Reactivities of Conjugated Dienes Towards the 1-Methyl-1-(methoxycarbonyl)ethyl Radical

1994 ◽  
Vol 47 (12) ◽  
pp. 2211 ◽  
Author(s):  
RA Lyons ◽  
E Senogles
Keyword(s):  
Methyl Methacrylate ◽  
Conjugated Dienes ◽  
Group Method ◽  
Poly Methyl Methacrylate ◽  
Ethyl Radical ◽  
Styrene Unit ◽  
End Group

The relative reactivities of butadiene, isoprene, 2,3-dimethylbutadiene, 2,3-diphenylbutadiene and methyl methacrylate with the 1-methyl-1-( methoxycarbonyl )ethyl radical have been evaluated by using the 'polymer end-group method', and the data obtained compared with those for the same monomers in their reactions with the poly(methyl methacrylate ), 1-cyano-1-methylethyl and 1-phenylethyl radicals. The observed reactivity trends can be explained by variations in the Q and e values for the monomers, and show that the 1-methyl-1-(methoxycarbonyl)ethyl radical is a good model for the poly(methyl methacrylate ) radical. Further results indicate that a penultimate styrene unit does not affect the reactivity of a poly(methyl methacrylate ) radical, whereas a penultimate methacrylonitrile unit does.

End-Group Analysis of Poly(methyl methacrylate) Prepared with Benzoyl Peroxide by 750 MHz High-Resolution1H NMR Spectroscopy

1997 ◽  
Vol 30 (22) ◽  
pp. 6754-6759 ◽  
Author(s):  
Koichi Hatada ◽  
Tatsuki Kitayama ◽  
Koichi Ute ◽  
Yoshio Terawaki ◽  
Takatsune Yanagida
Keyword(s):  
Nmr Spectroscopy ◽  
Methyl Methacrylate ◽  
Benzoyl Peroxide ◽  
Group Analysis ◽  
Poly Methyl Methacrylate ◽  
End Group

Synthesis of ω-End Group Functionalized Poly(methyl methacrylate)s via RAFT Polymerization

2010 ◽  
Vol 43 (18) ◽  
pp. 7453-7464 ◽  
Author(s):  
Barbara Sasso ◽  
Martyn Dobinson ◽  
Philip Hodge ◽  
Trevor Wear
Keyword(s):  
Methyl Methacrylate ◽  
Raft Polymerization ◽  
Poly Methyl Methacrylate ◽  
End Group

scholarly journals Thermolysis of RAFT-Synthesized Poly(Methyl Methacrylate)

2006 ◽  
Vol 59 (10) ◽  
pp. 755 ◽  
Author(s):  
Bill Chong ◽  
Graeme Moad ◽  
Ezio Rizzardo ◽  
Melissa Skidmore ◽  
San H. Thang
Keyword(s):  
Weight Loss ◽  
Methyl Methacrylate ◽  
1H Nmr Spectroscopy ◽  
Gel Permeation Chromatography ◽  
Dominant Mechanism ◽  
Elimination Process ◽  
Poly Methyl Methacrylate ◽  
Gel Permeation ◽  
Raft Agent ◽  
End Group

Thermolysis provides a simple and efficient way of eliminating thiocarbonylthio groups from RAFT-synthesized polymers. The course of thermolysis of poly(methyl methacrylate) (PMMA) prepared with dithiobenzoate and trithiocarbonate RAFT agents was followed by thermogravimetric analysis (TGA), 1H NMR spectroscopy, and gel permeation chromatography (GPC). The weight loss profile observed depends strongly on the RAFT agent used during polymer synthesis. PMMA with a methyl trithiocarbonate end group undergoes loss of that end group at ~180°C, at least in part, by a mechanism believed to involve homolysis of the C–CS2SCH3 bond and subsequent depropagation. In contrast, PMMA with a dithiobenzoate end appears more stable. Only the end group is lost at ~180°C and the dominant mechanism is proposed to be a concerted elimination process analogous to that involved in the Chugaev reaction.

Reactivities of Monomers Towards the 1-Methyl-1-(methoxycarbonyl)ethyl Radical

1994 ◽  
Vol 47 (12) ◽  
pp. 2201 ◽  
Author(s):  
RA Lyons ◽  
E Senogles
Keyword(s):  
Methyl Methacrylate ◽  
Methyl Acrylate ◽  
Poly Methyl Methacrylate ◽  
Ethyl Radical

The relative reactivities of acrylonitrile, methyl acrylate , methyl methacrylate and styrene towards the 1-methyl-1-( methoxycarbonyl )ethyl radical have been determined at 60°C, and the results compared with those for the poly (methyl methacrylate ) radical. The results for methyl acrylate suggest that the copolymerization of this monomer with methyl methacrylate is adequately described by a terminal mechanism. Those for styrene show that the presence of a penultimate styrene or methyl methacrylate unit in a poly(methyl methacrylate ) radical leads to a slightly greater preference for this radical to add styrene over methyl methacrylate compared to the 1-methyl-1-( methoxycarbonyl )ethyl radical. The results for methyl methacrylate and acrylonitrile suggest that the copolymerization of these monomers is probably best represented by a penultimate mechanism.

UV-Triggered End Group Conversion of Photo-Initiated Poly(methyl methacrylate)

2012 ◽  
Vol 45 (15) ◽  
pp. 5850-5858 ◽  
Author(s):  
Dominik Voll ◽  
Dmytro Neshchadin ◽  
Kai Hiltebrandt ◽  
Georg Gescheidt ◽  
Christopher Barner-Kowollik
Keyword(s):  
Methyl Methacrylate ◽  
Poly Methyl Methacrylate ◽  
End Group

Thermal stability of RAFT-based poly(methyl methacrylate): A kinetic study of the dithiobenzoate and trithiocarbonate end-group effect

2019 ◽  
Vol 164 ◽  
pp. 18-27 ◽  
Author(s):  
Marianna Z. Bekanova ◽  
Nikolay K. Neumolotov ◽  
Anastasija D. Jablanović ◽  
Anna V. Plutalova ◽  
Elena V. Chernikova ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Methyl Methacrylate ◽  
Kinetic Study ◽  
Group Effect ◽  
Poly Methyl Methacrylate ◽  
Thermal Stability Of ◽  
End Group
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