DOI: 10.5061/dryad.dr7sqvb9t
title: Data from: High-throughput generation of block copolymer libraries via click chemistry and automated chromatography

description: Designing block copolymers for specific applications is challenging
 because of the intricate relationship among molecular structure,
 self-assembly behavior, and bulk properties, which is compounded by a
 large design space that traditionally requires time-consuming, iterative
 synthesis. To overcome these challenges, here we report a library-based
 strategy leveraging an active ester-based block copolymer and automated
 chromatography which enables the high-throughput exploration of broad
 compositional and chemical landscapes without requiring sample-specific
 optimization. By integrating automated chromatography with robotic
 synthesis and orthogonal post-polymerization modification chemistry, we
 efficiently generated a diverse library of 90 well-defined block
 copolymers from a single as-synthesized “parent” copolymer. This adaptable
 method enables efficient access to materials with a wide range of
 compositions, molecular weights, functionalities, and properties. By
 integrating laboratory automation with click chemistry, these insights
 will accelerate the discovery and design of advanced block copolymers for
 high-performance applications.
description: High-Throughput Generation of Block Copolymer Libraries via Click
 Chemistry and Automated Chromatography Elizabeth A. Murphy,†,‡,# Katherine
 G. Roth,‡ Morgan W. Bates,# Megan C. Murphy,†,‡ Jerrick Edmund,†,§
 Christopher M. Bates,†,‡,%,# and Craig J. Hawker,†,‡,%,# †Materials
 Research Laboratory, ‡Department of Chemistry & Biochemistry,
 %Materials Department, §Department of Chemical Engineering, and
 #BioPACIFIC Materials Innovation Platform, University of California, Santa
 Barbara, California 93106, United States Macromolecules 2025, 58, 15,
 8369–8376 --- Data file names are labeled as Sample Name_Characterization
 Technique and organized into folders corresponding to figure and table
 numbers in the manuscript. --- Data is acquired from the following
 analytical characterization techniques. Details of the experimental design
 and data are highlighted below: Nuclear Magnetic Resonance Spectroscopy:
 Solution state nuclear magnetic resonance (NMR) spectra were recorded on a
 Varian 600 MHz spectrometer. Chemical shifts (δ) are reported in ppm
 relative to residual protio-solvent in CDCl3 (7.26 ppm). 1H, 13C, and 19F
 data has been collected. Data is shown as x column: chemical shift (ppm)
 and y column: intensity (a.u.). Data is in a .csv format. Size Exclusion
 Chromatography: Size-exclusion chromatography (SEC) was conducted on a
 Waters Alliance HPLC System, 2690 Separation Module using chloroform with
 0.25% triethylamine as the eluent with a flow rate of 0.35 mL/min.
 Refractive index traces from a Waters 2410 Differential Refractometer
 detector were used for estimates of the molar mass and dispersity relative
 to linear polystyrene standards with a chloroform mobile phase. Data is
 shown as x column: retention time (min) and y column: differential
 refractive index intensity (arb. units). Data is in a .txt format. Small
 Angle X-Ray Scattering: SAXS measurements of bulk samples were conducted
 using a custom-built high brilliance laboratory beamline for small and
 wide angle X-ray scattering (SAXS/WAXS) at the BioPACIFIC Materials
 Innovation Platform at University of California, Santa Barbara. The
 instrument is constructed using a high brightness liquid metal jet X-ray
 source (D2+ 70 kV from Excillum), a low background scatterless slit beam
 collimation system developed in house, and a 4-megapixel hybrid photon
 counting area detector (Eiger2 R 4M from Dectris) housed inside a 3
 meter-long vacuum vessel. Data is shown as x column: scattering q vector
 (A-1), y column: intensity (a.u.), and z column: error. Data is in a .txt
 format. Differential Scanning Calorimetry: Differential scanning
 calorimetry (DSC) was performed using a TA Instruments DSC Q2000 from –90
 to 55 °C at a heating/cooling rate of 10 °C/min using 3–5 mg of sample in
 a sealed Tzero aluminum pan. Data is shown as x column: time (min), y
 column: temperature (ºC), and z column: heat flow (W/g). Data is in a .txt
 format. Thermogravimetric Analysis: Thermogravimetric analysis (TGA) was
 performed under argon from 50 to 700 ºC on a TA Instruments Q500 at a
 heating rate of 10 ºC/min. Data is shown as first column: time (min);
 second column: temperature (ºC); third column: weight (mg); fourth column:
 weight percent (%) . Data is in a .txt format. Fourier Transform Infrared
 Spectroscopy: Fourier-transform infrared (FTIR) spectroscopy measurements
 were performed on a Thermo Nicolet iS10 FTIR spectrometer equipped with a
 Smart Diamond attenuated total reflectance (ATR) accessory. A background
 spectrum was obtained every 30 minutes and sample spectra were taken with
 64 scans in absorbance and transmittance mode. Data is shown as x column:
 absorbance or transmittance (arb. units) and y column: wavenumber
 (cm-1). Data is in a .txt format. Mass Recovery and Gradient Elution Data
 from Automated Chromatography: Automated flash chromatography was
 performed on a Biotage Selekt unit installed with an external evaporative
 light scattering detector (ELSD), using Biotage Sfär cartridge series (200
 g) eluted with suitable hexanes/ethyl acetate solvent gradients. All
 chromatographic solvents were ACS grade or better and used without further
 purification. In fractionation experiments, the mass recovery was taken as
 the ratio of the collected mass to the injected mass. Mass recovery data
 is shown as x column: test tube number and y column: mass (mg). Data is in
 a .txt format. --- All data presented in the main text of the manuscript
 can be found in the folder titled “Main Manuscript.” For detailed
 information about each dataset, please refer to the corresponding
 analytical characterization technique sections described above. Figure
 3: Size-exclusion chromatograms (SEC) of poly(ethyl
 acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer and
 precursors. Figure 4: 1H NMR spectra of the precursor poly(ethyl acrylate)
 homopolymer, E-TTC, and poly(ethyl
 acrylate)-b-poly(tetrafluorophenylacrylate) diblock copolymer before,
 EF-TTC, and after, EF-H, chain-end removal. Figure 5a: Mass recovery
 data. Chromatographic separation of a parent active ester diblock
 copolymer on a ≈11 g scale afforded a large library of fractionated
 samples with high mass recovery of 67%. Figure 5b: 1H NMR data to
 highlight volume fraction changes of fractions throughout the separation.
 Figure 7: 1H NMR data. Examples of distinct diblock copolymers obtained
 from a single as-synthesized parent material as evidenced by 1H NMR
 spectroscopy. Figure 8: Size-exclusion chromatograms of a representative
 block copolymer derived from a single chromatographically separated
 fraction indicate efficient functionalization with primary amines. Figure
 9: Differential scanning calorimetry thermograms (exo up, second heating
 cycle) of a representative block copolymer derived from a single
 fractionated sample. Representative thermograms are shown of the
 fractionated active-ester diblock copolymer and thiophene-2-ethylamine
 based diblock copolymer derived therefrom. --- All data presented in the
 supporting information of the manuscript can be found in the folder titled
 “Supporting Information.” For detailed information about each dataset,
 please refer to the corresponding analytical characterization technique
 sections described above. Figure S1: 1H NMR in CDCl3 of
 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR
 spectrometer. Figure S2: 1H NMR with fluorine decoupling in CDCl3 of
 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR
 spectrometer. Figure S3: 13C NMR in CDCl3 of 2,3,5,6-tetrafluorophenyl
 acrylate monomer using a 400 MHz NMR spectrometer. Figure S4: 19F NMR in
 CDCl3 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR
 spectrometer. Figure S5: FTIR spectrum of 2,3,5,6-tetrafluorophenyl
 acrylate monomer. Figure S6: 19F/1H heteronuclear correlation spectroscopy
 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR
 spectrometer. Figure S7: 19F/13C heteronuclear single quantum coherence of
 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR
 spectrometer. Figure S8: 19F/13C heteronuclear multiple bond correlation
 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR
 spectrometer. Figure S9: 1H NMR of poly(tetrafluorophenyl acrylate)
 homopolymer using a 600 MHz NMR spectrometer. Figure S10: . FTIR spectrum
 of poly(tetrafluorophenyl acrylate) homopolymer. Figure S11: 19F NMR of
 poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) with
 trithiocarbonate and proton chain end using a 600 MHz NMR spectrometer.
 Figure S14: Mass recovery data. Recovered mass was combined into 18
 distinct fractions with masses between ~400 –500 mg to have sufficient
 material for robotic functionalizations. Figure S15: 1H NMR spectra of as
 synthesized parent poly(ethyl acrylate)-bpoly(tetrafluorophenyl acrylate)
 diblock copolymer and a representative fractionated sample (fraction
 79–83) using a 500 MHz NMR spectrometer. Figure S16: 19F NMR spectra of as
 synthesized parent poly(ethyl acrylate)-bpoly(tetrafluorophenyl acrylate)
 diblock copolymer and a representative fractionated sample (fraction
 79–83) using a 500 MHz NMR spectrometer. Figure S17: Size-exclusion
 chromatograms (normalized differential refractive index signal, dRI) of
 fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate)
 diblock copolymers. Figure S18: Small-angle X-ray scattering patterns of
 fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate)
 diblock copolymers. Table S2: Molecular characterization data for
 well-defined fractionated diblock copolymers from parent poly(ethyl
 acrylate)-b-poly(tetrafluorophenyl acrylate). Data in table found in
 Figure S14 (mass recovery), Figure 5b (NMR data), and Figure S17 (SEC
 data) and is not duplicated. Figure S19: Representative 19F NMR spectra of
 fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate)
 diblock copolymer and 4-(trifluoromethyl)benzylamine functionalized sample
 derived therefrom using a 500 MHz NMR spectrometer. Figure S20:
 Representative 19F NMR spectra of fractionated poly(ethyl
 acrylate)-bpoly(tetrafluorophenyl acrylate) diblock copolymer and its
 derivative functionalized with thiophene-2-ethylamine,
 2-(4-chlorophenyl)ethylamine, and 4-methoxyphenethylamine (top to bottom)
 using a 500 MHz NMR spectrometer. Figure S21: Representative
 size-exclusion chromatograms (normalized differential refractive index
 (dRI) signals) of a set of functionalized diblock copolymers. SEC
 chromatograms are shown for a complete series of 18 distinct 2-(4-
 chlorophenyl)ethylamine-functionalized diblock copolymers. Figure S22:
 Size-exclusion chromatograms (normalized differential refractive index
 signal, dRI) of four functionalized block copolymers derived from a single
 fractionated sample (fraction 63–66). Chromatograms of
 amine-functionalized derivatives are shown in (a) orange for
 thiophene-2-ethylamine, (b) green for 4-(trifluoromethyl)benzylamine, (c)
 blue for 2-(4-chlorophenyl)ethylamine, and (d) purple for
 4-methoxyphenethylamine. Figure S23: TGA thermograph of
 poly(tetrafluorophenyl acrylate) homopolymer. Td5% is observed at 306 ºC.
 Figure S24: DSC thermogram (exo up, second heating cycle) of
 poly(tetrafluorophenyl acrylate) homopolymer. Glass transition temperature
 is observed at 58 ºC. Figure S25: TGA thermograph of poly(ethyl
 acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction
 89–94). Td5% is observed at 304 ºC. Figure S26: DSC thermogram (exo up,
 second heating cycle) of fractionated poly(ethyl
 acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction
 84–88). Glass transition temperature is observed at 25 ºC. Figure S27: TGA
 thermograph of thiophene-2-ethylamine functionalized diblock copolymer
 derived from fraction 84–88. Td5% is observed at 303 ºC. Figure S28: DSC
 thermogram (exo up, second heating cycle) of thiophene-2-ethylamine
 functionalized diblock copolymer derived from fraction 84–88. Glass
 transition temperatures are observed at –10 ºC and 69 ºC. Figure S29: TGA
 thermograph of 4-(trifluoromethyl)benzylamine functionalized diblock
 copolymer derived from fraction 84–88. Td5% is observed at 301 ºC. Figure
 S30: DSC thermogram (exo up, second heating cycle) of 4-
 (trifluoromethyl)benzylamine functionalized diblock copolymer derived from
 fraction 84– 88. Figure S31: TGA thermograph of
 2-(4-chlorophenyl)ethylamine functionalized diblock copolymer derived from
 fraction 84–88. Td5% is observed at 279 ºC. Figure S32: DSC thermogram
 (exo up, second heating cycle) of 2-(4- chlorophenyl)ethylamine
 functionalized diblock copolymer derived from fraction 84–88. Figure S33:
 TGA thermograph of 4-methoxyphenethylamine functionalized diblock
 copolymer derived from fraction 84–88. Td5% is observed at 291 ºC. Figure
 S34: DSC thermogram (exo up, second heating cycle) of
 4-methoxyphenethylamine functionalized diblock copolymer derived from
 fraction 84–88. Glass transition temperatures are observed at –7 ºC and 85
 ºC. Figure S35: Small-angle X-ray scattering patterns of fractionated
 poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer
 (fraction 84–88) and thiophene-2-ethylamine functionalized diblock
 copolymer derived from fraction 84–88. Figure S36: Small-angle X-ray
 scattering patterns of fractionated poly(ethyl
 acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction
 84–88) and 4-(trifluoromethyl)benzylamine functionalized diblock copolymer
 derived from fraction 84–88. Figure S37: Small-angle X-ray scattering
 patterns of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl
 acrylate) diblock copolymer (fraction 84–88) and
 2-(4-chlorophenyl)ethylamine functionalized diblock copolymer derived from
 fraction 84–88. Figure S38: Small-angle X-ray scattering patterns of
 fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate)
 diblock copolymer (fraction 84–88) and 4- methoxyphenethylamine
 functionalized diblock copolymer derived from fraction 84–88.