DOI: 10.5061/dryad.jh9w0vtmw
title: Scalable synthesis of degradable copolymers containing α‑lipoic 2 acid via miniemulsion polymerization

description: A robust method is described to synthesize degradable copolymers under
 aqueous miniemulsion conditions using α-lipoic acid as a cheap and
 scalable building block. Simple formulations of α-lipoic acid (up to 10
 mol%), n-butyl acrylate, surfactant, and costabilizer generate stable
 micelles in water with particle sizes &lt;200 nm. The ready
 availability of these starting materials facilitated performing
 polymerization reactions at large scales (4 L), yielding 600 g of
 poly(n-butyl acrylate–stat–α-lipoic acid) latexes that degrade under
 reducing conditions (250 kg mol–1 → 8 kg mol–1). Substitution of α-lipoic
 acid with ethyl lipoate further improves the solubility of dithiolane in
 n-butyl acrylate, resulting in copolymers that degrade to even lower
 molecular weights after polymerization and reduction. In summary, this
 simple and scalable strategy provides access to large quantities of
 degradable copolymers and particles using cheap and commercially available
 starting materials.
description: Molecular Characterization
 <em><sup>1</sup></em><em>H nuclear
 magnetic resonance spectroscopy</em> Solution
 state<em> </em><sup>1</sup>H nuclear magnetic
 resonance (NMR) spectra were recorded on a Varian VNMRS 600 MHz
 spectrometer. Chemical shifts (<em>δ</em>) are reported in ppm
 relative to residual protio solvent in CDCl<sub>3</sub> (7.26
 ppm). <em>Size-exclusion chromatography
 instrumentation</em> 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 for the mobile
 phase. Molar masses and molar mass dispersities (<em>Đ</em>)
 were determined against narrow PS standards (Agilent).
 <em>Thermal Characterization</em>
 Differential scanning calorimetry (DSC) was performed with a TA
 Instruments DSC Q2000 at a heating/cooling rate of 10 °C/min using 3–5 mg
 of sample in a sealed aluminum pan. Thermogravimetric analysis (TGA) was
 performed under nitrogen on a TA Instruments Q500 at a heating rate of 10
 °C min−1 with a sample size of ca. 4 mg.
 Dispersion Preparation and
 Characterization
 <em>Ultrasonication</em> Emulsions
 were prepared using a Fisher Scientific Ultrasonication Horn model FB-705.
 Sonications were performed using an ice bath with frequency 20 KHz,
 amplitude 20 m, pulsing on for 5 sec, then off for 10 sec for a
 total processing time of 5 minutes. <em>Dynamic
 Light Scattering</em> Dynamic light scattering
 (DLS) measurements of the emulsions were taken using a DynaPro NanoStar™
 from Wyatt Technology run at 25 C. The laser used emitted at
 662 nm with an intensity of 100 mW. Disposable 1 L cuvettes
 were used.
description: # Data For: Scalable synthesis of degradable copolymers containing
 α‑Lipoic 2 acid via miniemulsion polymerization Data was acquired from the
 following analytical characterization techniques: Molecular
 Characterization 1H nuclear magnetic resonance spectroscopy Solution state
 1H nuclear magnetic resonance (NMR) spectra were recorded on a Varian
 VNMRS 600 MHz spectrometer. Chemical shifts (δ) are reported in ppm
 relative to residual protio solvent in CDCl3 (7.26 ppm). Size-exclusion
 chromatography 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 for the mobile phase. Molar masses and molar mass
 dispersities (Đ) were determined against narrow PS standards (Agilent).
 Thermal Characterization Differential scanning calorimetry (DSC) was
 performed with a TA Instruments DSC Q2000 at a heating/cooling rate of 10
 °C/min using 3–5 mg of sample in a sealed aluminum pan. Thermogravimetric
 analysis (TGA) was performed under nitrogen on a TA Instruments Q500 at a
 heating rate of 10 °C min−1 with a sample size of ca. 4 mg. Dispersion
 Preparation and Characterization Dynamic Light Scattering Dynamic light
 scattering (DLS) measurements of the emulsions were taken using a DynaPro
 NanoStar™ from Wyatt Technology run at 25 °C. The laser used emitted at
 662 nm with an intensity of 100 mW. Disposable 1 μL cuvettes were used.
 All data is supplied in two columns (x,y) these columns refer to the x and
 y axis on each graph. Please refer to the manuscript and to the original
 graph for appropriate legends. All SEC data supplied is normalized to the
 peak being analyzed. All DLS is normalized to the peak being analyzed. ##
 Description of the data and file structure Data files are organized into
 two top-level folders. One for the main text manuscript figures and one
 for the supporting information. Data files can be opened as .txt or .csv
 using Excel or Google Sheets. Data files are organized as follows:\
 manuscript or SI -&gt; Figure number -&gt; figure sub-category (a, b, c,
 etc.) -&gt; 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 a part a and
 part b. In part a there are 2 traces. The data for the 5% LA is found:\
 MainTextFigures -&gt; Figure2 -&gt; Figure2a5LA-PartSize.txt Figure 2 has
 a part a and part b. In part b there are 2 traces. The data for the 10% LA
 is found:\ MainTextFigures -&gt; Figure2 -&gt; Figure2b10LA-PartSize.txt
 Figure S22 has two traces on a single graph. We read left to right. The
 traces are numbered left to right. The data for the light green trace on
 the right is found:\ SIFigures -&gt; S22-SEC -&gt; S22-PTFEASEC2.txt All
 SI folder titles give a brief description of the type of data found within
 (SEC, NMR, DSC, etc.) Figures that are pictures or illustrations are not
 included in the folders. This includes Figure 1, Figure 4a, Figure S9, and
 Figure S11 and Figure S25. The following describes the type of data
 contained in each figure: 2A: Dynamic light scattering (DLS) vs Time 2B:
 Raw Dynamic light scattering (DLS) 3A: Reaction Kinetics 3B: Molecular
 Composition 4B: Size-exclusion chromatography (SEC) 5A: Solubility Plot
 5B: Solubility Plot 6: Size-exclusion chromatography (SEC) S1: Dynamic
 light scattering (DLS) S2: Dynamic light scattering (DLS) S3:
 Size-exclusion chromatography (SEC) S4: Nuclear magnetic resonance (NMR)
 S5: Reaction Kinetics S6: Reaction Kinetics S7: Reaction Kinetics S8:
 Nuclear magnetic resonance (NMR) S10: Nuclear magnetic resonance (NMR)
 S12: Thermogravimetric analysis (TGA) S13: Size-exclusion chromatography
 (SEC) S14: Differential scanning calorimetry (DSC) S15: Nuclear magnetic
 resonance (NMR) S16: Nuclear magnetic resonance (NMR) S17: Nuclear
 magnetic resonance (NMR) S18: Nuclear magnetic resonance (NMR) S19:
 Nuclear magnetic resonance (NMR) S20: Size-exclusion chromatography (SEC)
 S21: Size-exclusion chromatography (SEC) S22: Size-exclusion
 chromatography (SEC) S23: Size-exclusion chromatography (SEC) S24:
 Size-exclusion chromatography (SEC) S26: Nuclear magnetic resonance (NMR)
 S27: Reaction Kinetics S28: Differential scanning calorimetry (DSC)