Synthesis of end-functionalized poly(methyl methacrylate) by organocatalyzed group transfer polymerization using functional silyl ketene acetals and α-phenylacrylates
The present study describes the α- and ω-end-functionalization of poly(methyl methacrylate)s (PMMAs) by organocatalyzed group transfer polymerization (GTP) using both functional silyl ketene acetal (SKA) initiators and α-phenylacrylate terminators. The syntheses of structurally defect-free α-end-fun...
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Published in | Polymer chemistry Vol. 6; no. 10; pp. 1830 - 1837 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
01.01.2015
|
Subjects | |
Online Access | Get full text |
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Summary: | The present study describes the α- and ω-end-functionalization of poly(methyl methacrylate)s (PMMAs) by organocatalyzed group transfer polymerization (GTP) using both functional silyl ketene acetal (SKA) initiators and α-phenylacrylate terminators. The syntheses of structurally defect-free α-end-functionalized PMMAs with hydroxyl, ethynyl, vinyl, and norbornenyl groups (HO-PMMA, HCC-PMMA, H
2
CCH-PMMA, and NB-PMMA, respectively) were achieved by either the
N
-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide-(Me
3
SiNTf
2
-) or
t
-Bu-P
4
-catalyzed GTP of MMA using functional trimethyl SKAs (
1a–1d
). On the other hand, the ω-end-functionalized PMMAs with ethynyl, hydroxyl, vinyl, and bromo groups (PMMA-CCH, PMMA-OH, PMMA-CHCH
2
, and PMMA-Br, respectively) were for the first time obtained by the Me
3
SiNTf
2
-catalyzed GTP of MMA followed by a termination reaction using functional α-phenylacrylates (
2a–2d
). All the polymerizations produced end-functionalized PMMAs with controlled molar masses, narrow dispersities, and defect-free polymer structures as designed. The quantitative incorporation of functionalities into the α- or ω-end of the PMMAs was confirmed by the
1
H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) measurements. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1759-9954 1759-9962 |
DOI: | 10.1039/C4PY01564A |