Data for: Versatile synthesis of siloxane-based graft copolymers with tunable grafting density
Data files
Sep 26, 2023 version files 117.68 MB
Abstract
A versatile synthetic platform is reported that affords high molecular weight graft copolymers containing polydimethylsiloxane (PDMS) backbones and vinyl-based side chains with excellent control over molecular weight and grafting density. The synthetic approach leverages thiol–ene click chemistry to attach an atom-transfer radical polymerization (ATRP) initiator to a variety of commercially available poly(dimethylsiloxane-co-methylvinylsiloxane) (PDMS-co-PVMS), followed by controlled radical polymerization with a wide scope of vinyl monomers. Selective degradation of the siloxane backbone with tetrabutylammonium fluoride confirmed the controlled nature of side-chain growth via radical polymerization, yielding targeted side-chain lengths for copolymers containing up to 50% grafting density and overall molecular weights in excess of 1 MDa. In addition, by using a mixture of thiols, grafting density and functionality can be further controlled by tuning initiator loading along the backbone. For example, solid-state fluorescence of the graft copolymers was achieved by incorporating a thiol-containing fluorophore along the siloxane backbone during the thiol–ene click reaction. This simple synthetic platform provides facile control over the properties of a wide variety of grafted copolymers containing flexible PDMS backbones and vinyl polymer side chains.
README: Data for Versatile synthesis of siloxane-based graft copolymers with tunable grafting density
https://doi.org/10.5061/dryad.5tb2rbp9v
The dataset provides tables corresponding to each plot in both the main text and the supplemental information. Datasets include nuclear magnetic resonance (NMR) spectroscopy traces, size-exclusion chromatography (SEC), 2-D SEC plots, and differential scanning calorimetry (DSC) data.
The data is organized into two folders: Main text figures and SI figures. In the Main Text folder, there are subfolders corresponding to each main text figure containing plots. In the folders corresponding to main text figures, there are .xlsv files containing a single dataset corresponding to the figure trace listed in the title of the file. In the SI figures folder, there are .xlsv files titled with the figure they correspond to. For SI figures that contain multiple traces, there are multiple tabs in the .xlsv file that are titled with the corresponding trace label.
Description of the data and file structure
NMR data is provided as two columns of data corresponding to ppm and intensity (arbitrary units) in the first and second columns, respectively.
SEC data is provided as two columns of data corresponding to retention time (minutes) and signal (arbitrary units) in the first and second columns, respectively. The signal is collected from a differential refractive index (dRI) detector or from a photodiode array (PDA) detector. The PDA detector collects light absorbance (arbitrary units) over a range of wavelengths (nm). The displayed wavelength is given in the figure caption.
2-D SEC data is given as a spreadsheet where the top row is light wavelength (nm) starting at column B, the first column is the retention time (minutes) starting at column 3, and the light absorbance (arbitrary units) is in cells B3:DQ15003.
DSC data is included in Figure S35 and Figure S36. Data includes heat flow (W/g) and temerature (°C) in the first and second columns, respectively.
Methods
Size-exclusion chromatography (SEC) was performed on a Waters Alliance HPLC system using two Tosoh TSKgel SuperHZM-N columns containing 3 µm crosslinked polystyrene beads and a Waters 2410 Differential Refractometer with chloroform with 0.25% triethylamine as the mobile phase at a 0.35 mL/min flow rate. Number and weight average molecular weights (Mn and Mw respectively) were calculated based on polystyrene standards to calculate dispersity (Ð), unless otherwise specified. Plotted data has been baseline-corrected and normalized. The dRI signal for SEC data in Figure 2 corresponding to the top two traces has been inverted to facilitate comparison with the bottom trace.
1H nuclear magnetic resonance (NMR) spectroscopy was performed on a Varian 600 MHz using a relaxation delay (d1) of 4.8 seconds. 13C NMR spectroscopy was performed on a Bruker 500 MHz with a d1 of 10 seconds. Signal ppm values were shifted to match the solvent signal to 7.257 ppm in 1H and 77.17 ppm in 13C.
Differential Scanning Calorimetry (DSC) was performed on a TA instrument Q2000 DSC with three repeated cycles: heating from 25 °C to 150 °C, cooled to -150 °C, and heated to 150 °C. Only the final cycle is plotted. Glass transition values were calculated using a function in the Trios software.