This readme.txt file was generated on 2024-07-29 Recommended citation for the data: Liang, Shuang; Krajovic, Daniel, M.; Hoehn, Brenden, D.; Ellison, Christopher, J.; Hillmyer, Marc, A. (2024). Supporting data for Engineering Aliphatic Polyester Block Copolymer Blends for Hydrolytically Degradable Pressure Sensitive Adhesives. Retrieved from the Data Repository for the University of Minnesota (DRUM). https://doi.org/10.13020/6jz3-sd14 ------------------- GENERAL INFORMATION ------------------- 1. Title of Dataset: Supporting data for Engineering Aliphatic Polyester Block Copolymer Blends for Hydrolytically Degradable Pressure Sensitive Adhesives 2. Author Information Author Contact: Marc A. Hillmyer (hillmyer@umn.edu) Christopher J. Ellison (cellison@umn.edu) Name: Shuang Liang Institution: University of Minnesota Email: sliang@umn.edu ORCID: 0000-0002-0457-5819 Name: Daniel M. Krajovic Institution: University of Minnesota Email: krajo001@umn.edu ORCID: 0000-0001-5311-1941 Name: Brenden D. Hoehn Institution: University of Minnesota Email: hoehn073@umn.edu ORCID: 0000-0002-3879-8842 Name: Christopher J. Ellison Institution: University of Minnesota Email: cellison@umn.edu ORCID: 0000-0002-0393-2941 Name: Marc Hillmyer Institution: University of Minnesota Email: hillmyer@umn.edu ORCID: 0000-0001-8255-3853 3. Date published or finalized for release: 2024-07-29 4. Date of data collection: 2022-08-10 - 2024-5-10 5. Geographic location of data collection: All data : University of Minnesota, Minneapolis MN 6. Information about funding sources that supported the collection of the data: This work was supported by the Avery Dennison Corporation with contributions from the National Science Foundation Center for Sustainable Polymers at the University of Minnesota, which is a National Science Foundation–supported Center for Chemical Innovation (CHE–1901635). 7. Overview of the data (abstract): This work aimed to explore aliphatic polyester triblock copolymers of poly(L–lactide)–block–poly(γ–methyl–ε–caprolactone)–block–poly(L–lactide) (LML) and associated blends with renewable tackifier in pressure-sensitive adhesive (PSA) formulations and investigate effects of tackifier, composition, and processing history on microstructural, thermal, mechanical, and adhesive properties of the PSAs. After solvent casting and two–step annealing at 170 °C for 60 min and 100 °C for 5 min, LML–based PSAs showed stable and competitive adhesion properties when compared to commercial PSAs, which we attribute to both microphase separation and crystallinity in the poly(L–lactide) end blocks. Moreover, theses LML–based PSA formulations are hydrolytically degradable into water soluble or dispersible compounds at 45 ℃ under basic conditions within 30 days, offering the possibility of sustainable end–of–life scenarios for example through industrial composting. -------------------------- SHARING/ACCESS INFORMATION -------------------------- 1. Licenses/restrictions placed on the data: CC0 1.0 Universal http://creativecommons.org/publicdomain/zero/1.0/ 2. Links to publications that cite or use the data: Liang, Shuang; Krajovic, Daniel, M.; Hoehn, Brenden, D.; Ellison, Christopher, J.; Hillmyer, Marc, A. Engineering Aliphatic Polyester Block Copolymer Blends for Hydrolytically Degradable Pressure Sensitive Adhesives ACS Appl. Polym. Mater. 2025. 3. Was data derived from another source? No If yes, list source(s): 4. Additional related data collected that was not included in the current data package: None. 5. Are there multiple versions of the dataset? No 6. Terms of Use: Data Repository for the U of Minnesota (DRUM) By using these files, users agree to the Terms of Use. https://conservancy.umn.edu/pages/drum/policies/#terms-of-use --------------------- DATA & FILE OVERVIEW --------------------- File List: Filename: SI-Engineering Aliphatic Polyester Block Copolymer Blends for Hydrolytically Degradable Pressure Sensitive Adhesives.zip Filename: README.txt Abbreviation Descriptions and data files organization: General Notes: File names use the naming conventions from the paper and are listed in folders by Figure number. PSA - pressure-sensitive adhesive PγMCL - poly(γ–methyl–ε–caprolactone) PLLA - poly(L–lactide) LML - poly(L–lactide)–block–poly(γ–methyl–ε–caprolactone)–block–poly(L–lactide) aLML - poly(lactide)–block–poly(γ–methyl–ε–caprolactone)–block–poly(lactide) Small Angle X-ray Scattering - SAXS Nuclear Magnetic Resonance - NMR Size Exclusion Chromatography - SEC Thermogravimetric Analysis - TGA Differential Scanning Calorimetry - DSC Atomic Force Microscopy - AFM Files Contained: Files are sorted by Analysis Type and Figure. SAXS Data - The raw data is in .csv files to be opened in Excel for the 1D spectra. SEC data - The raw data is in .csv Excel format for each polymer. TGA data - The raw data is in .csv Excel format. Adhesion test data - The raw data is shown in .csv files. DSC - The raw data is given in .csv files. NMR data - The raw data is given in .csv files. AFM data - The raw data is given in .tif files. Contact angle data - The raw data is given in .tif files. -------------------------- METHODOLOGICAL INFORMATION -------------------------- Description of methods used for collection, generation, and processing of data: Experimental methods are described in the supporting information word document for Supporting data for Engineering Aliphatic Polyester Block Copolymer Blends for Hydrolytically Degradable Pressure Sensitive Adhesives. People involved with sample collection, processing, analysis and/or submission: Shuang Liang, Daniel M. Krajovic, Brenden D. Hoehn: Data collection, processing, analysis, and submission. Christopher J. Ellison and Marc A. Hillmyer: Data analysis and submission. -------------------------- EXPERIMENTAL METHODS -------------------------- Materials 1,4–benzenedimethanol (BDM) was purchased from Sigma–Aldrich, recrystallized in toluene, and sublimed overnight at 100 °C under reduced pressure before storing under nitrogen in the glovebox. γ–Methyl–ε–caprolactone (γMCL) was purchased from Renewable Solutions, LLC and purified through fractional distillation at 70–100 °C under dynamic vacuum around 100 mTorr. L–lactide was provided by NatureWorks, LLC and recrystallized from anhydrous ethyl acetate (3 times) and anhydrous toluene (3 times) under an argon atmosphere and filtered in open air. After recrystallization, the L–lactide was dried for 24 hours at 80 °C under vacuum and was stored under a dry nitrogen atmosphere in a glovebox. D,L–lactide was purchased from Sigma–Aldrich and recrystallized from anhydrous ethyl acetate (3 times) and anhydrous toluene (3 times), and filtered in open air. After recrystallization, the D,L–lactide was dried for 72 hours under vacuum at room temperature, and stored under nitrogen atmosphere in a glovebox. Tin (II) 2–ethylhexanoate (Sn(Oct)2) was purchased from Sigma–Aldrich and purified through three fractional distillations under dynamic vacuum, 145–170 °C with fractions cooled in a suspension of dry ice and isopropyl alcohol. The products were dried overnight under vacuum, purged with argon, and stored under nitrogen in the glovebox. Deuterium–chloroform (CDCl3) was purchased from Cambridge Isotope Laboratories. Anhydrous toluene was obtained from a JC Meyer solvent drying system and stored over 4–Å molecular sieves under argon before using. The rosin ester tackifier (Sylvalite 2E 80HP) was provided by Kraton Chemical. All other chemicals were purchased from Sigma–Aldrich and used without further purification unless noted. Synthesis of poly(L–lactide)–block–poly(γ–methyl–ε–caprolactone)–block–poly(L–lactide) (LML) and poly(D,L–lactide)–block–poly(γ–methyl–ε–caprolactone)–block–poly(D,L–lactide) (aLML) triblock copolymers To synthesize PγMCL macroinitiator, γMCL (10 g, 78 mmol), BDM (21.5 mg, 0.155 mmol) and Sn(Oct)2 (32 mg, 0.078 mmol) were added into a pressure vessel equipped with a Teflon–coated magnetic stir bar under nitrogen atmosphere in the glove box. The vessel was sealed, taken out of the glove box, and placed in an oil bath preheated to 130 °C. After 90 minutes, the vessel was cooled in an ice bath to stop the reaction and dilute with chloroform. The solution was then precipitated into cold methanol (3 times) and hexanes (3 times) before drying in vacuum oven at room temperature for 48 hours. To synthesize LML triblock copolymers, PγMCL (9g, 0.135 mmol) was dissolved in anhydrous toluene (41.6 ml) in the glove box under nitrogen atmosphere for 48 hours to achieve homogenous solution. L–lactide (3 g, 20.8 mmol) and Sn(Oct)2 (9.4 mg, 0.0208 mmol) were then added into the solution in a pressure vessel equipped with a Teflon–coated magnetic stir bar. The vessel was sealed, taken out of the glove box, and placed in an oil bath preheated to 130 °C. After 90 minutes, the vessel was cooled in an ice bath to stop the reaction and dilute with chloroform. The solution was then precipitated into cold methanol (3 times) and hexanes (3 times) before drying in vacuum oven at room temperature for 48 hours. To synthesize aLML triblock copolymers, similar process was used except replacing L–lactide monomer with D,L–lactide monomer. Pressure–sensitive adhesives (PSAs) preparation Polymers with or without tackifier were dissolved in chloroform overnight to yield a 20 wt% homogeneous solution, followed by casting onto a poly(ethylene terephthalate) (PET) substrate (40 µm, ChemInstruments) using a wire wound rod. The PSAs were then dried under continuous nitrogen flow at room temperature for 48 hours. The thickness of the dried film was roughly 80 µm. Afterwards, for the one–step annealing process, the PSAs were put into an oven preheated to 170 °C for 1 hour under nitrogen atmosphere, followed by rapid quenching (approximately 35 °C/min) to room temperature on a cold metal substrate. Subsequently, for the two–step annealing process, the PSAs were put into an oven preheated to 100 °C for 5 minutes under nitrogen atmosphere, followed by rapid quenching (approximately 35 °C/min) to room temperature on a cold metal substrate. Adhesive testing Standard test methods used for peel adhesion, loop tack adhesion, and shear strength were PSTC:101, ASTM:D1695, and PSTC:107, respectively. The polished stainless steel panel (PSTC 304 BRT, 18 Gauge), high density polyethylene (HDPE, Polymershapes) panels, and PET panels (Polymershapes) were used as the adherent for adhesion testing. The adhesion data of the sticky note (Postit®, 3M), office tape (Scotch® Magic™, 3M), duct tape and electrical tape (Scotch® 22, 3M) were used from previous reports. 180° peel test: a 1 cm wide strip of the PSA coated–PET film was adhered to a panel using a 2 kg rubber roller. The sample was tested by a Shimadzu ASG–X tensile tester at a peel rate of 305 mm min−1. The peel force was recorded as the plateau force. The test was performed at least three times and averaged across the samples except for the occasional clear outlier samples. Loop tack test: a 1 cm wide strip of the PSA coated–PET film was made into a teardrop shaped loop and mounted to the upper grip of the tensile tester while a stainless steel panel was mounted on the lower grip. Then the loop was gently lowered forming a contact area of 1 cm × 1.5–2 cm. The tack force was monitored while the upper grip was lifted at a rate of 305 mm min−1. The tack force was recorded as the maximum measure force. The test was performed at least three times and averaged across the samples except for the occasional clear outlier samples. Shear resistance test: A PSA coated–PET film was adhered to a stainless steel panel forming a contact area of 2.54 cm × 2.54 cm, and pressed by a rubber roller. A 1000 g weight was applied to the sample, and the time to failure (weight drop) was recorded, and averaged across at three samples. Hydrolytic degradation test PSA coated–PET film was cut into 1 cm × 1 cm square before dispersing in a vial of either ~20 ml 1 M NaOH aqueous solution. The vials were then put into an oven at 45 °C. 50 µL aliquots at various time points were taken out from the vials, diluted with 9950 µL deionized water before total organic carbon (TOC) measurement using a Shimadzu TOC–L analyzer. Controlled experiments of PET films were also conducted under same conditions. Note: Hydrolytic degradation tests were also conducted in ~20 mL 1M HCl aqueous solution and ~20 mL artificial seawater (pH = 8.1) at 45 °C. Although the PSA films turned translucent (after 15 days in 1M HCl aqueous solution and after 7 days in artificial seawater, respectively), no significant change in TOC measurement was observed in 90 days. Flory–Fox equation to calculate glass transition temperature of the mixed domain 1/T_(g,mixed domain) = ∑_i▒w_i/T_(g,i) Where Tg,mixed domain is the glass transition temperature of the mixed domain, Tg,i is the glass temperature of component i and wi is the weight fraction of component i. Given immiscible PγMCL and PLA domains, the expected Tg,mixed domain is calculated assuming all tackifier preferentially mixes with PγMCL domain, and by Tg, PγMCL and Tg,tackifier with different weight fraction. Characterization 1H–NMR and 13C–NMR spectra were obtained from 400 MHz Bruker Avance III HD with SampleXpress. Size exclusion chromatography (SEC) was performed with tetrahydrofuran (THF) as mobile phase (25 °C, 1 mL min–1) on an Agilent Infinity 1260 HPLC system equipped with Waters Styragel HR columns, a Wyatt HELEOS–II multiangle laser light scattering (MALS) detector, and a Wyatt Optilab T–rEX S7 differential refractive index detector. Small–angle X–ray scattering (SAXS) was acquired from 15–minute exposures in the Characterization Facility, University of Minnesota, using a Xenocs instrument (Ganesha). Thin film samples were prepared from specific processing history before mounting up on Kapton tape and exposure at room temperature. Thermogravimetric analysis (TGA) was performed on a TA Instruments Q500 (heating rate: 10 °C min−1) under nitrogen atmosphere. Thermal properties were investigated via differential scanning calorimetry measurements under nitrogen flow with a TA Instruments Discovery Series differential scanning calorimeter and a refrigerated cooling system. Linear viscoelastic properties were probed via small amplitude oscillatory shear (SAOS) experiments with a TA ARES G2 rheometer and 8 mm parallel–plate fixture. Samples were processed after specific history before molding on the rheometer at 80 °C. All experiments were carried out in the linear viscoelastic region determined by dynamic strain sweep at –20 °C and a frequency of 1 rad s–1. Frequency sweeps were performed at 1 % strain and temperatures from –20 to 80 °C. Previous reports demonstrated that an LML triblock with similar molar mass showed an order–disorder transition (ODT) around 180 ℃.5 However, the ODT is inaccessible in our case due to the degradation of both PγMCL and PLLA during the measurement. Therefore, it is difficult to rheometrically resolve the morphological evolution of the blends after different processing histories. Atomic force microscopy (AFM) was conducted on thin film samples on a Bruker Nanoscope V Multimode 8 open–loop system in peak force mode. Water contact angle measurements were made by mounting samples on a glass slide and analyzing them with a microscopic contact angle meter (Kyowa Interface Science Co). The images were captured by a horizontal camera with a high magnification lens and processed using FAMAS image processing software. ---------------------------------- DATA TREE ---------------------------------- Supporting data for Engineering Aliphatic Polyester BCP Blends for Hydrolytically Degradable PSAs.zip Figure 1_THF SEC_aLML (78.5, 0.22).csv Figure 1_THF SEC_LML (76.6, 0.27).csv Figure 1_THF SEC_PMCL (62.2).csv Figure 1_THF SEC_PMCL (67.3).csv Figure 2 RT SAXS_Solvent casting & 1-step annealing.csv Figure 2 RT SAXS_Solvent casting & 2-step annealing.csv Figure 2 RT SAXS_Solvent casting.csv Figure 3 RT SAXS_SAXS patterns.csv Figure 4 DSC.csv Figure 5a linear viscoelastic properties.csv Figure 5b linear viscoelastic properties.csv Figure 6a Peel adhesion forces.csv Figure 6b Loop tack forces.csv Figure 7 TOC.csv Figure S1 1H NMR_PMCL (62.2).csv Figure S1 1H NMR_PMCL (67.3).csv Figure S2 1H NMR_aLML (78.5, 0.22).csv Figure S2 1H NMR_LML (76.6, 0.27).csv Figure S3 13C NMR_LML (76.6, 0.27).csv Figure S3 13C NMR_PMCL (62.2).csv Figure S4 1H NMR_LML (76.6, 0.27) solvent casting & 1-step annealing.csv Figure S4 1H NMR_LML (76.6, 0.27) solvent casting & 2-step annealing.csv Figure S4 1H NMR_LML (76.6, 0.27) solvent casting.csv Figure S5 THF SEC_LML (76.6, 0.27) solvent casting & 1-step annealing.csv Figure S5 THF SEC_LML (76.6, 0.27) solvent casting & 2-step annealing.csv Figure S5 THF SEC_LML (76.6, 0.27) solvent casting.csv Figure S6 RT SAXS.csv Figure S7 AFM_LML(76.6, 0.27)_33 wt% tackifier after casting-annealing.tif Figure S7 AFM_LML(76.6, 0.27)_33 wt% tackifier after casting.tif Figure S7 Contact angle_LML(76.6, 0.27)_33 wt% tackifier after casting-anneal.tif Figure S7 Contact angle_LML(76.6, 0.27)_33 wt% tackifier after casting.tif Figure S8 TGA.csv Figure S9 DSC.csv Figure S10 DSC.csv Figure S11 DSC.csv Figure S12 Linear viscoelastic properties.csv Figure S13 Linear viscoelastic properties.csv Figure S14.csv Figure S15a Peel adhesion forces.csv Figure S15b Loop tack forces.csv Figure S16.csv Figure S17.csv Figure S18.csv Figure S19.csv Figure S20 DSC.csv Figure S21.csv Figure S22.csv Figure S23.csv Figure S24a.csv Figure S24b.csv Figure S25.csv Readme.txt