This README_Supplementary_Data.txt file was generated on 2025-03-04 by Kathrin Marina Eckert (kathrin.eckert@tuhh) ------------------- GENERAL INFORMATION ------------------- Name: Kathrin Marina Eckert (ORCID: 0000-0002-8454-4886) Role/Function: Data collector (main contact person) Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Email: kathrin.eckert@tuhh.de Name: Simon Müller (ORCID: 0000-0003-1684-6994) Role/Function: Data collector Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Name: Gerrit A. Luinstra (ORCID: 0000-0003-4602-8319) Role/Function: Principal Investigator Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Name: Irina Smirnova (ORCID: 0000-0003-4503-4039) Role/Function: Principal Investigator (alternative contact person) Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Email: irina.smirnova@tuhh.de Name: Jana Katharina Ruhstrat Role/Function: Data collector Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Name: Robin Stumpenhagen Role/Function: Data collector Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Name: Alena Sophie Steinbach Role/Function: Data collector Institution: Institute of Thermal Separation Processes, Hamburg University of Technology Address: Eißendorfer Straße 38, 21073 Hamburg, Germany Date of data collection: July 2023 - December 2023 Location of data collection: Institute of Thermal Separation Processes, Hamburg University of Technology, Hamburg, Germany Funding: This project is funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – SFB 1615 – 503850735. --------------------------- SHARING/ACCESS INFORMATION --------------------------- Title of data set: "Data Supplement to the Article 'Exploring pNIPAM Lyogels: Experimental Study on Swelling Equilibria in Various Organic Solvents and Mixtures, Supported by COSMO-RS Analysis'" DOI of data set: https://doi.org/10.15480/882.15026 Related publication: Kathrin Marina Eckert et al. Exploring pNIPAM Lyogels: Experimental Study on Swelling Equilibria in Various Organic Solvents and Mixtures, Supported by COSMO-RS Analysis. (2024) DOI of related article: https://doi.org/10.1016/j.fluid.2024.114182 Please cite the accepted version of this publication in case you use the data. Keywords: swelling behaviour, phase equilibria, polymer, solvent-induced, COSMO-RS, stimuli-responsive gels, smart reactors --------------------- DATA & FILE OVERVIEW --------------------- ### 1. Chemicals.csv (creation date: 18.07.2024, version: 01) - **Description:** List of chemicals used in the study. - **Columns:** - Chemical: Name of the chemical used - Purity: Purity of the chemical used - Supplier: Supplier of the chemical used - CAS-Nr.: CAS-Nr. of the chemical used ### 2. Degree_of_swelling_pure_solvents.csv (creation date: 18.07.2024, version: 01) - **Description:** Degree of swelling (DoS) of pNIPAM lyogels in pure organic solvents. - **Columns:** - Organic solvent: Organic solvent in which the gel is immersed. - Degree of swelling [g/g]: Degree of swelling measured after equilibration. ### 3. Degree_of_swelling_binary_mixtures.csv (creation date: 18.07.2024, version: 01) - **Description:** Degree of swelling (DoS) of pNIPAM lyogels in binary solvent mixtures composed of esters and alcohols or carboxylic acids. - **Columns:** - Solvent Mixture: The solvents present in this analysis. - Mole fraction of alcohol / carboxylic acid [-]: Mole fraction of the alcohol or carboxylic acid in the liquid after equilibratin. - Degree of swelling [g/g]: Degree of swelling measured after equilibration. ### 4. Degree_of_swelling_esterification.csv (creation date: 18.07.2024, version: 01) - **Description:** Degrees of swelling of pNIPAM lyogels in ternary solvent mixtures. - **Columns:** - Reactive system: Components in the esterification system (solvents in the liquid phase). - Relative ester concentration [mol/mol]: Concentration of ester in the liquid phase after equilibration. - Degree of swelling [g/g]: Degree of swelling measured after equilibration. ### 5. IDACS_pnipam_derivates_organicsolvents.csv (creation date: 18.07.2024, version: 01) - **Software:** COSMOtherm 2020 - **Description:** Infinite dilution activity coefficients (IDACs) of pNIPAM derivatives in various organic solvents. - **Columns:** - Organic Solvent: Name of the organic solvent in which the IDACs of pNIPAM are calculated. - Monomer: IDACs for monomer at infinite dilution. - Monomer (with single bond): IDACs for monomer (with single bond) at infinite dilution. - Trimer: IDACs for trimer at infinite dilution. - Pentamer: IDACs for pentamer at infinite dilution. - Heptamer: IDACs for heptamer at infinite dilution. ### 6. Hydrogen_bonds_pnipam_derivates_organicsolvents.csv (creation date: 18.07.2024, version: 01) - **Software:** COSMOtherm 2020 - **Description:** Hydrogen bond interaction energies of pNIPAM derivatives in organic solvents at infinite dilution. - **Columns:** - Organic Solvent: Name of the organic solvent in which the hydrogen bonds with pNIPAM are calculated. - Monomer [kJ/mol]: Hydrogen bond interaction energies of monomer at infinite dilution. - Monomer (with single bond) [kJ/mol]: Hydrogen bond interaction energies of monomer with single bond at infinite dilution. - Trimer [kJ/mol]: Hydrogen bond interaction energies of trimer at infinite dilution. - Pentamer [kJ/mol]: Hydrogen bond interaction energies of pentamer at infinite dilution. - Heptamer [kJ/mol]: Hydrogen bond interaction energies of heptamer at infinite dilution. ### 7. VdW_pnipam_derivates_organic_solvents.csv (creation date: 18.07.2024, version: 01) - **Software:** COSMOtherm 2020 - **Description:** Van der Waals interaction energies of pNIPAM derivatives in organic solvents at infinite dilution. - **Columns:** - Organic Solvent,Monomer [kJ/mol]: Name of the organic solvent in which the Van der Waals interaction energies with pNIPAM are calculated. - Monomer (with single bond) [kJ/mol]: Van der Waals interaction energies of monomer (with single bond) at infinite dilution. - Trimer [kJ/mol]: Van der Waals interaction energies of trimer at infinite dilution. - Pentamer [kJ/mol]: Van der Waals interaction energies of pentamer at infinite dilution. - Heptamer [kJ/mol]: Van der Waals interaction energies of heptamer at infinite dilution. ### 8. Smiles.csv (creation date: 18.07.2024, version: 01) - **Description:** Name of structures for theoretical analysis (IDACs and interaction energies) in COSMO-RS. - **Columns:** - pNIPAM derivate: Name of pNIPAM derivate. - Smiles: Smiles code of the components used for COSMOconv calculations. --------------------------- METHODOLOGICAL INFORMATION --------------------------- The methodolical information can be found in the publication. 1. Experimental Methods Gel Synthesis: For the preparation of hydrogels, 2.175 g NIPAM and 0.030 g MBA were dissolved in 21 g of deionized water, and degassed with nitrogen for 30 min. Subsequently, 2.5 mg of sodium persulfate and ammonium persulfate were each dissolved in 1 mL of deionized water and added to the mixture. The hydrogel monoliths were cast in syringes (BRAUN, 10 mL) and covered with PARAFILM (SigmaAldrich). Swelling Equilibria: The hydrogel was sliced into cylindrical segments measuring 1–1.5 cm in height and 1.5 cm in diameter; inhomogeneous end pieces were discarded. For the solvent exchange from water to pure solvents or mixtures, the gel monoliths were immersed in the desired solvent or mixture and shaken, followed by two additional solvent exchange steps with fresh solvents each after 24 h. Subsequently, the lyogel was equilibrated for 48 h at 25 °C (± 0.1 °C) in a water bath (Grant OLS200). The required timeframe was determined based on previous experiments. The solvent exchange to pure esters or 1-butanol required an additional solvent exchange to ethanol due to the limited miscibility of the solvents with water. In solvent mixtures, the hydrogel was first immersed in the solvent in which lower swelling behavior of the gel was obtained. Afterwards, the solvent exchange to the requested solvent mixture was performed. The equilibrated lyogels were dried at 40 °C (± 0.1 °C) under vacuum conditions for 48 h to calculate the mass-specific degree of swelling: Dos = m_gel/m_polymer (mass of equilibrated gel / mass of dried polymer). For the investigation of the swelling behavior during an ongoing esterification reaction, solutions of equimolar mixtures of the reactants were prepared with different concentrations of esters. The concentrations of esters in these mixtures were set to be equivalent to specific conversion rates of the reactions. In this work, solvent-polymer interactions were investigated by preparing solvent mixtures based on conversion rates of the esterification reaction, without carrying out the reaction experimentally. This method enabled the investigation of the influence of solvent-polymer interactions in the occurring solvent mixtures during the reaction, separate from the reaction kinetics. The solvent mixtures were prepared water-free to avoid the formation of a second solvent phase. Solvent Composition Analysis: The composition of the solvent phase after the equilibration of the gel was analyzed by GC (GC 7890 B, Agilent Technologies). The GC method can be described as follows: (i) column: DB-WAX, Agilent Technologies (30 m x 0.25 mm x 0.5 μm); (ii) column oven temperature: 353.2 °C for 2 min; (iii) temperature ramps: 413.2 K (rate = 10 K/min) for 2 min, 483.2 K (rate = 20 K/min) for 5.5 min, (iv) carrier gas: nitrogen; (v) flow rate: 25 mL/min; (vi) injector temperature: 523.2 K; and (vii) detector temperature: 533.2 K. Injection was done with a split ratio of 400 and the injection volume was 1 μL. 2. Theoretical Methods: The COSMO-RS calculations were performed using the software COSMOtherm (BP_TZVPD_FINE_19). For the conformer search COSMOconf (v3.0) with Turbomole (v. 6.6) was used. In this work, different monomer and oligomer structures (trimer, pentamer, heptamer) were investigated and their infinite dilution activity coefficients (IDAC) in various organic solvents ln(γi∞) were calculated using COSMOtherm. ----------------- RESEARCH CONTEXT ----------------- This study focuses on modeling and analyzing the swelling behavior of pNIPAM-based lyogels for potential applications in chemical and biochemical reactors. By integrating smart lyogel technology, the research aims to contribute to the development of intelligent reactor systems. Thermodynamic modeling, specifically using the gE model COSMO-RS, is applied to monomers and oligomers of pNIPAM to examine the correlation between solvent-polymer interactions and the degree of swelling. The study highlights the influence of hydrogen bonding and solvent polarity on the swelling behavior in both pure and mixed solvent systems, including those relevant to esterification reactions. ---------------------------------- EXPLANATION OF MEASURED VARIABLES ---------------------------------- Degree of swelling: Dos = m_gel/m_polymer (mass of equilibrated gel / mass of dried polymer), is the relative swelling of gel in certain solvent or mixtures. This value must be > 1 g/g. Infinitive dilution activity coefficient: IDAC, is calculated using COSMOtherm and describes the activity coefficient of one component at infinite diluted state in the other component. From this, miscibility preferences can be derived or in terms of gels, their swelling properties. Hydrogen bond interaction energy: Calculated using COSMOtherm, describes the interaction energy between two components with one at the state of infinitive dilution [kJ/mol]. Van der Waals interaction energy: Calculated using COSMOtherm, describes the interaction energy between two components with one at the state of infinitive dilution [kJ/mol].