DOI: 10.5061/dryad.tx95x6b54
title: Data for: Facile Preparation of Tunable Polyborosiloxane Networks via Hydrosilylation

description: Polyborosiloxanes are used in a variety of fields due to their unique and
 useful dynamic properties. Traditionally, crosslinked polyborosiloxanes
 are prepared by incorporating boric acid into siloxane pre-polymers, a
 process that is time consuming, energy intensive, and challenging due to
 the immiscibility of the reagents. Here, we report a versatile synthetic
 method to rapidly cure polyborosiloxane networks via hydrosilylation of
 chain-end or backbone functionalized polydimethylsiloxane (PDMS)
 derivatives with an inexpensive trivinylboronate. Networks synthesized
 from these readily available building blocks cure in ~2 minutes at
 convenient temperatures (e.g., 90 °C) and exhibit enhanced viscoelastic
 behavior when compared to traditional polyborosiloxane networks fabricated
 via the conventional condensation route. By virtue of using efficient
 hydrosilylation chemistry, another key advantage of this synthetic
 platform is the ability to synthesize dynamic polyborosiloxanes with
 different network connectivity by simply using silicones with Si–H
 moieties placed at the chain ends (telechelic) or distributed throughout
 the repeat-unit structure (copolymers). The availability of other alkenes
 amenable to hydrosilylation provides an additional formulation handle to
 synthesize mixed dynamic–static networks with tunable control over stress
 relaxation and solvent resistance. In summary, the synthetic approach
 disclosed herein is a simple and accessible platform for preparing dynamic
 polyborosiloxanes with tunable material properties.
description: Chemical Characterization Attenuated total
 reflectance Fourier transform infrared spectroscopy (ATR-FTIR) spectra
 were collected on a Nicolet is10 spectrometer with a diamond ATR
 accessory. All spectra were collected with 64 scans and a 4 cm–1
 resolution in absorbance mode, baseline corrected, and displayed in
 transmittance mode. Proton nuclear magnetic resonance (NMR) spectra were
 taken on a Varian Unity Inova AS600 600MHz at 25 °C with 16 scans and a
 relaxation delay (d1) of 15 seconds. Solution state 11B, 13C, and 29Si NMR
 spectra were taken on a Bruker Avance NEO 500 MHz at 25 °C. 11B spectra
 used a d1 value of 2 seconds and 64 scans. 13C used a d1 value of 2
 seconds and 256 scans. 29Si used a d1 value of 60 seconds and 32 scans.
 Solid-state NMR (ssNMR) spectra were taken on a Bruker AVANCE500 WB with
 magic-angle spinning (MAS) of 14 kHz at 30° pulses. Samples were ground
 and placed into a 4 mm Bruker zirconia rotor. 29Si ssNMR spectra were
 captured with a d1 of 30 seconds and 4856 scans. 11B ssNMR spectra were
 captured with a d1 of 6 seconds and 12248 scans and background
 corrected. Rheology In order to
 limit hydrolysis and oxygen permeation, rheology experiments were
 performed immediately after network fabrication.  25 mm discs were punched
 out of cured networks at 140 °C, immediately transferred onto the 25 mm
 stainless steel parallel plate within the environmental chamber of the
 rheometer, and held at the same temperature. Rheology experiments were
 performed on a strain-controlled TA Instruments ARES-G2 rheometer affixed
 with a forced convection oven in a nitrogen atmosphere.  Stress relaxation
 experiments were performed by rapidly applying a 1% strain and monitoring
 the decay in measured stress over time. Three samples
 were measured to ensure consistency (Figures S2, S3, and S4). The applied
 strain was confirmed to be in the linear viscoelastic regime of each
 sample (Figure S5). For sample series requiring multiple temperatures,
 rheology experiments were performed from high to low temperature. Single
 (Equation 1) and stretched (Equation 2) exponential fits were applied to
 stress relaxation data measurements for a polyborosiloxane network
 prepared from a 5 kDa telechelic Si–H functional PDMS precursor.
 Representative fits are shown in Figure S6, and averaged values with
 standard deviations are shown in Tables S2 and S3. Normalized modulus
 values were obtained by normalizing the dataset by the value of the
 modulus at time 0.1 second.
description: # Facile Preparation of Tunable Polyborosiloxane Networks via
 Hydrosilylation
 [https://doi.org/10.5061/dryad.tx95x6b54](https://doi.org/10.5061/dryad.tx95x6b54) This dataset provides tabulated values for all the plots featured in the associated manuscript, including rheometry, nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, swelling, and gel fraction data. The dataset is separated into two primary folders, each containing subfolders corresponding to each manuscript figure from the main text or supplementary information. ## Description of the data and file structure This dataset is separated into two primary folders—MainText and SupplementaryInformation. Each primary folder contains subfolders corresponding to a Figure. Each of these subfolders contains one or more CSV files corresponding to a plot contained in that Figure. Within each CSV file, data are arranged in columns with labels of the structure FigureName_TraceIdentifier_axis.