Telechelic dithiol copolymers as tunable building blocks for synthesizing multiblock materials
Data files
Dec 11, 2024 version files 1.11 MB
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MainTextFigures.zip
1.11 MB
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README.md
4.12 KB
Abstract
A new strategy is reported to access α,ω‐dithiol polymer building blocks with tunable molecular weights and compositions for the preparation of random multiblock copolymers based on styrenic, acrylic, and siloxanes. This facile synthetic approach provides access to dithiols through a two‐step process: (1) an initial copolymerization of vinyl monomers with ethyl lipoate followed by (2) disulfide bond reduction, producing dithiol terminated polymer products. Thiol‐terminated polymers are easily prepared over a wide range of molecular weights (2–32 kDa) by simply controlling the feed ratio of vinyl monomer to ethyl lipoate. Mixtures of these linear dithiol‐terminated building blocks were repolymerized via oxidative coupling to create random multiblock copolymers with high molecular weights (68–95 kDa) and controlled degradability. In summary, this approach for preparing and recombining telechelic dithiol polymers creates opportunities to manipulate the mechanical and physical properties of multiblock copolymers using a synthetically simple and versatile platform.
README: Title of Dataset: Telechelic dithiol copolymers as tunable building blocks for synthesizing multiblock materials
This deposit includes the data necessary to reproduce all figures in the associated manuscript, except for figures that consist of pictures or illustrations.
Data is acquired from the following analytical characterization techniques:
Characterization methods
1H nuclear magnetic resonance (NMR) spectroscopy
1H-NMR spectra were collected on a Bruker Avance NEO 500 MHz at 25 °C using chloroform-d as a deuterated solvent.
Size-exclusion chromatography (SEC) instrumentation
Size-exclusion chromatography (SEC) was performed on a Waters instrument using a differential refractive index detector and two Tosoh columns (TSKgel SuperHZM-N, 3 μm polymer, 150 × 4.6 mm) with THF at 35 °C or chloroform containing 0.25% TEA at 35 °C for the mobile phase. Molar mass and molar mass dispersities (Đ) were determined against narrow PS standards (Agilent).
Differential scanning calorimetry (DSC)
DSC was performed on a TA Instruments Q2000 DSC with three repeated cycles between −150 and +150 °C at a constant rate of 10 °C/min. Only the second heating scan is shown.
Small-angle X-ray scattering (SAXS)
SAXS measurements were performed on a custom-built SAXS diffractometer housed at the University of California, Santa Barbara. The sample-to-detector distance was 1.7 m with a fixed wavelength of 1.54 Å. For all SAXS experiments, a silver behenate standard was used to calibrate the scattering angles. Two-dimensional (2D) data were reduced by azimuthal averaging to give I(q), where I is the intensity in arbitrary units, q = |q| =4πλ–1 sin(θ/2) is the magnitude of the scattering wave vector, λ is the wavelength of the incident beam, and θ is the scattering angle. Two data points (at q = 0.15438 Å and q = 0.16026 Å), which correspond to two known dead pixels on the detector, were excised from the resulting data set for clarity.
Mechanical tensile testing
For uniaxial extension tensile tests, a Teflon dog bone mold was used to shape samples on a Carver press (Wabash, IN) 10 kPA at 160 °C for 10 min and then cooled (gauge depth = 0.5 mm, gauge width = 1.5 mm, gauge length = 10 mm, transition zone radius = 2.5 mm). Uniaxial tensile testing was performed on a TA.XT Plus Connect Texture Analyzer with a 50N load cell using the Miniature Tensile grips (TA-96B) from the manufacturer. Grip surfaces were covered with adhesive backed foam padding to avoid damage to tensile bars and slip of samples from the grips. Samples were deformed at 0.1 mm/s until failure. Mechanical testing of polymer samples was performed in triplicate and representative data is included in the main text.
## Description of the data and file structure
Data files are organized into folders. Main text manuscript figures which are numbered according to the figure then further divided into each individual trace.
All data can be opened as a .csv or .txt files using a text editor or a spreadsheet program.
Data files are organized as follows:
MainTextFigures -> Figure number -> figure sub-category (a, b, c, etc.) -> trace
For figures with multiple traces on a single graph the traces are numbered reading top to bottom left to right or titled as given by the legend on the figure itself.
For Example:
Figure 2 has two graphs with 3 traces each. We start with the left graph, then read top to bottom. The data for the 32 kDa, 5 mol% ELP PS is found:
MainTextFigures -> Figure2 -> Fig2a-PS5mol_pct.txt
Figure 2 has two graphs with 3 traces each. We start with the left graph, then read top to bottom. The data for the 11 kDa, 40 mol% ELP PnBA is found:
MainTextFigures -> Figure2 -> Fig2e-PnBA40mol_pct.txt
All data is supplied in two columns (x,y) these columns refer to the x and y axis on each graph. Refer to the manuscript and to the original graph for appropriate legends.
All SEC data supplied is normalized to the peak being analyzed.
Figures 2 and 4 display size-exclusion chromatography (SEC) data, and Figure 6 illustrates uniaxial tension (UAT) measurements.
Methods
Characterization methods
1H nuclear magnetic resonance (NMR) spectroscopy
1H-NMR spectra were collected on a Bruker Avance NEO 500 MHz at 25 °C using chloroform-d as a deuterated solvent.
Size-exclusion chromatography (SEC) instrumentation
Size-exclusion chromatography (SEC) was performed on a Waters instrument using a differential refractive index detector and two Tosoh columns (TSKgel SuperHZM-N, 3 μm polymer, 150 × 4.6 mm) with THF at 35 °C or chloroform containing 0.25% TEA at 35 °C for the mobile phase. Molar mass and molar mass dispersities (Đ) were determined against narrow PS standards (Agilent).
Differential scanning calorimetry (DSC)
DSC was performed on a TA Instruments Q2000 DSC with three repeated cycles between −150 and +150 °C at a constant rate of 10 °C/min. Only the second heating scan is shown.
Small-angle X-ray scattering (SAXS)
SAXS measurements were performed on a custom-built SAXS diffractometer housed at the University of California, Santa Barbara. The sample-to-detector distance was 1.7 m with a fixed wavelength of 1.54 Å. For all SAXS experiments, a silver behenate standard was used to calibrate the scattering angles. Two-dimensional (2D) data were reduced by azimuthal averaging to give I(q), where I is the intensity in arbitrary units, q = |q| =4πλ–1 sin(θ/2) is the magnitude of the scattering wave vector, λ is the wavelength of the incident beam, and θ is the scattering angle. Two data points (at q = 0.15438 Å and q = 0.16026 Å), which correspond to two known dead pixels on the detector, were excised from the resulting data set for clarity.
Mechanical tensile testing
For uniaxial extension tensile tests, a Teflon dog bone mold was used to shape samples on a Carver press (Wabash, IN) 10 kPA at 160 °C for 10 min and then cooled (gauge depth = 0.5 mm, gauge width = 1.5 mm, gauge length = 10 mm, transition zone radius = 2.5 mm). Uniaxial tensile testing was performed on a TA.XT Plus Connect Texture Analyzer with a 50N load cell using the Miniature Tensile grips (TA-96B) from the manufacturer. Grip surfaces were covered with adhesive backed foam padding to avoid damage to tensile bars and slip of samples from the grips. Samples were deformed at 0.1 mm/s until failure. Mechanical testing of polymer samples was performed in triplicate and representative data is included in the main text.