DOI: 10.5061/dryad.41ns1rnm6
title: Accelerated discovery and mapping of block copolymer phase diagrams

description: Block copolymers are widely used in many applications due to their
 spontaneous self-assembly into a variety of nanoscale morphologies.
 However, a grand challenge in navigating this diverse and ever-growing
 array of possible structures is the accelerated discovery, design, and
 implementation of new materials. Here, we report a versatile and efficient
 strategy to accelerate materials discovery by rapidly building expansive,
 high-quality, and detailed block copolymer libraries through a combination
 of controlled polymerization and chromatographic separation. To illustrate
 the potential of this approach, a family of 16 parent diblock copolymers
 was synthesized and separated, leading to over 300 distinct and
 well-defined samples at the multigram scale. The resulting materials span
 a wide range of compositions with exceptional resolution in volume
 fraction and domain spacing that allows for the impact of monomer design
 on polymer self-assembly to be elucidated. Phase behavior that can be
 gleaned from these libraries includes the precise location of order–order
 boundaries and the identification of morphologies with extremely narrow
 windows of stability. This user-friendly, scalable, and automated approach
 to discovery significantly increases the availability of well-defined
 block copolymers with tailored molecular weights, molar-mass dispersities,
 compositions, and segregation strengths, accelerating the study of
 structure–property relationships in advanced soft materials.
description: Nuclear Magnetic Resonance Spectroscopy: Solution
 state<em> </em><sup>1</sup>H nuclear magnetic
 resonance (NMR) spectra were recorded on a Varian 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). 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. 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 UCSB. 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.  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.
description: Accelerated Discovery and Mapping of Block Copolymer Phase Diagrams
 Elizabeth A. Murphy,†,‡,# Stephen J. Skala,†,%,# Dimagi Kottage,†,‡
 Phillip A. Kohl,†,# Youli Li,†,# Cheng Zhang,†,Ͱ Craig J. Hawker,,†,‡,%,#
 and Christopher M. Bates,,†,‡,§,%,# †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 ͰAustralian Institute for Bioengineering and Nanotechnology
 and Centre for Advanced Imaging University of Queensland, Brisbane,
 Queensland 4072, Australia *** 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: 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:
 chemical shift (ppm) and y: intensity (a.u.). 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: retention time (min) and y: differential refractive index
 intensity (a.u.). 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:
 scattering q vector (A-1), y: intensity (a.u.), and z: error. 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: time (min), y: temperature (ºC), and z:
 heat flow (W/g). Data shown in the main text of the manuscript is located
 in the folder "Main text": Figure 2: NMR spectroscopy data (1H)
 of representative D-1F, D-5F, D-9F, and D-12F parent diblock copolymers.
 Figure 3: SEC chromatograms of representative D-1F, D-5F, D-9F, and D-12F
 parent diblock copolymers and their corresponding homopolymers. Folders
 organized by sections Figure 3a, 3b, 3c, 3d. Figure 4: NMR spectroscopy
 data (1H) of D-1F,-57% D-5F-28%, D-9F-36%, and D-12F-39% parent diblock
 copolymers and fractions derived therefrom. Folders organized by sections
 Figure 4a, 4b, 4c, 4d with D-1F,-57% D-5F-28%, D-9F-36%, and D-12F-39%
 data respectively. Figure 5: SAXS and NMR spectroscopy data (1H) for D-1F,
 D-5F, D-9F, and D-12F phase diagrams. Folders organized by phase diagram
 with subfolders of characterization technique (NMR and SAXS). Figure 6:
 SAXS data of D-12F-31% parent diblock copolymer and fractions derived
 therefrom. Figure 7: SAXS data of D-5F-67% parent diblock copolymer and
 fractions derived therefrom. Data shown in the supporting information of
 the manuscript is located in the folder "Supporting
 Information": Figure S1: NMR spectroscopy data (1H) of 2-fluoroethyl
 acrylate monomer. Figure S2: NMR spectroscopy data (13C) of 2-fluoroethyl
 acrylate monomer. Figure S3: NMR spectroscopy data (19F) of 2-fluoroethyl
 acrylate monomer. Figure S4: NMR spectroscopy data (1H) of representative
 D homopolymer. Figure S5: NMR spectroscopy data (1H) of 1F homopolymer.
 Figure S6: NMR spectroscopy data (19F) of 1F homopolymer. Figure S7: NMR
 spectroscopy data (1H) of 5F homopolymer. Figure S8: NMR spectroscopy data
 (19F) of 5F homopolymer. Figure S9: NMR spectroscopy data (1H) of 9F
 homopolymer. Figure S10: NMR spectroscopy data (19F) of 9F homopolymer.
 Figure S11: NMR spectroscopy data (1H) of 12F homopolymer. Figure S12: NMR
 spectroscopy data (19F) of 12F homopolymer. Figure S13: NMR spectroscopy
 data (1H) of a representative D-1F diblock copolymer. Figure S14: NMR
 spectroscopy data (19F) of a representative D-1F diblock copolymer. Figure
 S15: NMR spectroscopy data (1H) of a representative D-5F diblock
 copolymer. Figure S16: NMR spectroscopy data (19F) of a representative
 D-5F diblock copolymer. Figure S17: NMR spectroscopy data (1H) of a
 representative D-9F diblock copolymer. Figure S18: NMR spectroscopy data
 (19F) of a representative D-9F diblock copolymer. Figure S19: NMR
 spectroscopy data (1H) of a representative D-12F diblock copolymer. Figure
 S20: NMR spectroscopy data (19F) of a representative D-12F diblock
 copolymer. Figure S21: DSC thermogram of 1F homopolymer. Figure S22: DSC
 thermogram of 5F homopolymer. Figure S23: DSC thermogram of 9F
 homopolymer. Figure S24: DSC thermogram of 12F homopolymer. Table S1: SEC
 chromatograms of 1F, 5F, 9F, and 12F homopolymers. NMR spectroscopy data
 (1H) for 1F, 5F, 9F, and 12F homopolymers shown in Figures S5, S7, S9,
 S11, respectively. Table S3: SEC chromatograms of D-1F-16%, D-1F-27%,
 D-1F-36%, D-1F-57% parent diblock copolymers. NMR spectroscopy data (1H)
 for and SAXS data shown in Figure 5, D-1F phase diagram and not duplicated
 in the supporting information folder. Tables S4, S5, S6, S7: NMR
 spectroscopy data (1H) and SAXS data shown in Figure 5, D-1F phase diagram
 and not duplicated in the supporting information folder as this is the
 same data but shown in a tabulated form in the supporting information.
 Table S8: SEC chromatograms of D-5F-14%, D-5F-27%, D-5F-28%, D-5F-40%,
 D-5F-67% parent diblock copolymers. NMR spectroscopy data (1H) for and
 SAXS data shown in Figure 5, D-5F phase diagram and not duplicated in the
 supporting information folder as this is the same data but shown in a
 tabulated form in the supporting information. Tables S9, S10, S11, S12,
 S13: NMR spectroscopy data (1H) and SAXS data shown in Figure 5, D-5F
 phase diagram and not duplicated in the supporting information folder as
 this is the same data but shown in a tabulated form in the supporting
 information. Table S14: SEC chromatograms of D-9F-27%, D-9F-36%, D-9F-50%
 parent diblock copolymers. NMR spectroscopy data (1H) for and SAXS data
 shown in Figure 5, D-9F phase diagram and not duplicated in the supporting
 information folder as this is the same data but shown in a tabulated form
 in the supporting information. Tables S15, S16, S17: NMR spectroscopy data
 (1H) and SAXS data shown in Figure 5, D-9F phase diagram and not
 duplicated in the supporting information folder as this is the same data
 but shown in a tabulated form in the supporting information. Table S18:
 SEC chromatograms of D-12F-31%, D-12F-32%, D-12F-39%, D-12F-68% parent
 diblock copolymers. NMR spectroscopy data (1H) for and SAXS data shown in
 Figure 5, D-12F phase diagram and not duplicated in the supporting
 information folder as this is the same data but shown in a tabulated form
 in the supporting information. Tables S19, S20, S21, S22: NMR spectroscopy
 data (1H) and SAXS data shown in Figure 5, D-9F phase diagram and not
 duplicated in the supporting information folder as this is the same data
 but shown in a tabulated form in the supporting information. Figures S27,
 S28, S29, S30: SAXS data shown in Figure 5, D-1F phase diagram and not
 duplicated in the supporting information folder as this is the same data
 but shown in a plotted form in the supporting information. Figures S31,
 S32, S33, S34, S35: SAXS data shown in Figure 5, D-5F phase diagram and
 not duplicated in the supporting information folder as this is the same
 data but shown in a plotted form in the supporting information. Figures
 S36, S37, S38 : SAXS data shown in Figure 5, D-9F phase diagram and not
 duplicated in the supporting information folder as this is the same data
 but shown in a plotted form in the supporting information. Figures S39,
 S40, S41, S42 : SAXS data shown in Figure 5, D-12F phase diagram and not
 duplicated in the supporting information folder as this is the same data
 but shown in a plotted form in the supporting information. Figure S43: SEC
 chromatograms of D-5F-27% parent diblock copolymer with A15 structure and
 fraction 60 derived therefrom with sigma structure.