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4 protocols using poly ethylene glycol methyl ether acrylate

1

Synthesis of Polyethylene Glycol-Silane Compound

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Example 4

To a 50 ml, round-bottomed flask, 2.279 mmol of bis(3-triethoxysilylpropyl)amine (Gelest Co.) and 5 ml of ethanol were added for dissolving, and 2.279 mmol of poly(ethylene glycol) methyl ether acrylate (Sigma-Aldrich Co.) was added thereto, followed by stirring at room temperature in nitrogen conditions for 8 hours. After finishing the reaction, solvents were removed under a reduced pressure and distilled at 120° C. under a reduced pressure to obtain 2.13 mmol of a 2,5,8,11,14,17,20,23,26-nonaoxaoctacosane-28-yl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate compound of Formula (iv) (Yield 93.5%). 1H NMR spectroscopic data of separated 2,5,8,11,14,17,20,23,26-nonaoxaoctacosane-28-yl 3-(bis(3-(triethoxysilyl)propyl)amino)propanoate are as follows.

[Figure (not displayed)]

1H-NMR (500 MHz, CDCl3) δ 4.17-4.15 (t, 2H), δ 3.78-3.73 (m, 12H), δ 3.60-3.59 (m, 32H), δ 3.50-3.48 (m, 2H), δ 3.32 (s, 3H), δ 2.74-2.71 (m, 2H), δ 2.37-2.34 (t, 6H), δ 1.50-1.43 (m, 4H), δ 1.19-1.15 (t, 18H), δ 0.54-0.50 (m, 4H)

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2

Synthesis of Functional Polymers via ATRP

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2-(Methylthio)ethanol (≥99%) was purchased from Alfa Aesar. Hydrogen peroxide solution (30%) was purchased from Fisher Scientific. Acrylic acid (≥99%), tin(II) 2-ethylhexanoate (SnII(EH)2, ≥95%), methyl acrylate (≥99%), n-butyl acrylate (≥99%), poly(ethylene glycol) methyl ether acrylate (OEGA, average Mn = 480), N-(3-(dimethylamino)propyl)-N′-ethylcarbodiimide hydrochloride (EDC, ≥99%), N,N-dimethylamino pyridine (DMAP, ≥99%), copper bromide (≥99.99%), ascorbic acid, (AA, ≥99%), divinylbenzene (DVB, technical grade, 80%), and ethyl α-bromoiso-butyrate (EBiB, 98%) were purchased from Sigma-Aldrich. Acrylic acid was distilled under vacuum before use. All acrylate monomers were passed through basic alumina columns before use. Tris(2-pyridylmethyl)amine (TPMA) was synthesized according to previous procedures.41 (link) All solvents and other chemicals are of reagent quality and were used as received unless special treatments discussed below were applied.
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3

Synthesis of Diverse Acrylate and Methacrylate Monomers

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Glyceryl monomethacrylate (GMA; 98%, supplied
by GEO Specialty Chemicals), poly(ethylene glycol) methyl ether acrylate
(PEGA, Mn = 480, Sigma-Aldrich), poly(ethylene
glycol) methyl ether methacrylate (PEGMA, Mn = 950, Sigma-Aldrich), acrylic acid (AA, 99%; Fisher), methacrylic
acid (MAA, ≥99%; Merck), lauryl acrylate (LA, >98%, TCI
Chemicals), iso-octyl acrylate (iOA, >90%;
Sigma-Aldrich),
2-ethylhexyl acrylate (EHA, Alfa Aesar, 98%), iso-bornyl acrylate (iBA 99%; Alfa Aesar), tert-butyl acrylate (tBuA, 99%; Alfa Aesar), 3,5,5-trimethylhexyl
acrylate (TMHA; Sigma-Aldrich), 3,5,5-trimethylhexyl methacrylate
(TMHMA, ABCR), and tert-octyl acrylamide (OAA; supplied
by ABCR, Germany) were all used as received. Asoisobutyronitrile (AIBN)
was recrystallized twice from mEthanol. Ethanol (99.8%, Fisher), mEthanol
(>99%, Sigma-Aldrich), THF, and n-heptane (>99%,
Sigma-Aldrich) were used as received. 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic
acid (DDMAT, 98%) was purchased from Sigma-Aldrich and used as received.
MilliQ water was obtained from an Elga Elgastat Option 3A Water Purifier
system.
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4

Synthesis and Characterization of Functional Polymers

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Acrylic acid (AA, 99%, anhydrous, Sigma-Aldrich), acetonitrile (ACN, 99.8%, Sigma-Aldrich), 4-methoxyphenol (MEHQ, 99%, Sigma-Aldrich), diethyl ether (DEE, >98%, Sigma-Aldrich), ethanol (>99.8%, Sigma-Aldrich), 1,4-dioxane (>99%, Sigma-Aldrich), Luperox® TBH70X tertbutyl hydroperoxide solution (tBuOOH, 70% wt.% in H2O, Sigma-Aldrich), L-ascorbic acid (AsAc, Sigma Aldrich), 2-methoxyethylamine (MeOEtNH2, 99%, Sigmal-Aldrich), poly(ethylene glycol) methyl ether acrylate (Sigma-Aldrich), 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4methylmorpholinium chloride (DMTMM-HCl, >96%, Sigma-Aldrich) and 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium tetrafluoroborate (DMTMM-BF4, 97%, Sigma Aldrich) were used as purchased without further purification. 2-Methyl-2-oxazoline (MeOx, 98%, Sigma-Aldrich) was distilled to dryness over barium oxide (BaO) and stored in a nitrogen atmosphere.
The chain transfer agent (CTA), 2-(((butylthio)-carbonothioyl)thio)-propanoic acid was prepared according to a literature procedure. 35 Amine-terminated poly(2-ethyl-2-oxazoline) (PEtOxNH2) was synthesized following a literature procedure. 36 2-(pyridyldithio)-ethylamine hydrochloride (PDS) was obtained from Speed Chemical, China. Cyanine5 amine was purchased from Lumiprobe. CellLight™ ER-GFP, BacMam 2.0 and CellLight™ Golgi-GFP, BacMam 2.0 were purchased from Thermo Fisher Scientific.
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