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2 protocols using 2 ethylhexyl methacrylate

1

Synthesis of Methacrylate Polymer Precursors

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Methyl
methacrylate (MMA, 99%), ethyl methacrylate
(EMA, 99%), n-butyl methacrylate (BMA, 99%), n-hexyl methacrylate (HMA, 99%), DMAEMA (99%), and MAA (99.5%)
were purchased from Sigma-Aldrich (Gillingham, U.K.) and were passed
through a basic alumina column to remove inhibitor prior to polymerization.
2-Ethylhexyl methacrylate (EHMA, 98%) was purchased from Alfa Aesar
(Heysham, U.K.), and its inhibitor was removed using an alumina column.
Isopropanol (IPA, 99.9%), triethanolamine (TEA, 99%), 4,4′-azobis(4-cyanovaleric
acid) (ACVA), 1,4-dioxane (99.5%), trimethylsilyldiazomethane solution
(2.0 M in diethyl ether), benzyl bromide (BzBr, 98%), and deuterated
acetone were purchased from Sigma-Aldrich. Deuterated chloroform (CDCl3) and deuterated dimethyl sulfoxide (DMSO-d6) for NMR spectroscopy measurements were purchased from
VWR (Lutterworth, U.K.). Deionized water was obtained using an Elgastat
Option 3A water purifier (Elga, High Wycombe, U.K.). 4-Cyano-4-(2-phenylethanesulfanylthiocarbonyl)sulfanylpentanoic
acid (PETTC) used for RAFT polymerization was prepared and purified
in-house, as reported previously.35 (link) Unless
stated otherwise, all materials were used as received.
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2

Synthesis and Characterization of Functionalized Polymers

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4-Methylumbelliferone, 7-hydroxy-4-methylcoumarin, 11-bromoundecanol, diethylether, ethanol, acetone, p-toluenesulfonyl chloride, piperidine, pyridine, methacryloyl chloride, 2,2'-azobis(2methylpropionitrile) (AIBN) MgSO4, potassium carbonate (K2CO3) and dodecanethiol (DDT) were purchased from Sigma Aldrich and used without further purification. 2-ethylhexyl methacrylate was purchased from Alfa Aesar. 2-Methyl-2-oxazoline (MOXA), 2-phenyl-2oxazoline (PhOXA), 2-n-butyl-2-oxazoline (BuOXA) and acetonitrile were distilled over CaH2 just prior to use. methacryloyl chloride was distilled under reduced pressure before use. Coumarin tosylate (CoumOTs) was synthesized and purified by recrystallization according to previously published protocols 26 . Acetonitrile and chloroform were distilled over CaH2 and stored in nitrogen.
All other commercial reagents and solvents were used as received. Ultrapure water was obtained from an ELGA Purelab Flex system (resistivity greater than 18.2 MΩ.cm) and was filtered on 0.2 m RC filters just before use. 1 H and 13 C NMR Spectra were recorded using a Bruker Avance 300 MHz spectrometer.
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