DOI: 10.5061/dryad.5tb2rbp9v
title: Data for: Versatile synthesis of siloxane-based graft copolymers with tunable grafting density

description: 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.
description: 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
 (<em>M</em><sub>n</sub> and
 <em>M</em><sub>w</sub> respectively) were
 calculated based on polystyrene standards to calculate dispersity
 (<em>Ð</em>), 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. 
 <sup>1</sup>H nuclear magnetic resonance (NMR)
 spectroscopy was performed on a Varian 600 MHz using a relaxation delay
 (d<sub>1</sub>) of 4.8 seconds. <sup>13</sup>C NMR
 spectroscopy was performed on a Bruker 500 MHz with a
 d<sub>1</sub> of 10 seconds. Signal ppm values were shifted to
 match the solvent signal to 7.257 ppm in <sup>1</sup>H and
 77.17 ppm in <sup>13</sup>C. 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. 
description: # Data for Versatile synthesis of siloxane-based graft copolymers with
 tunable grafting density
 [https://doi.org/10.5061/dryad.5tb2rbp9v](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.