--> Project: Microphase Separation of Highly Amphiphilic, Low N Polymers by Photoinduced Copper-Mediated Polymerization, Achieving Sub-2 nm Domains at Half-Pitch --> Folder Structure: The files are organised by technique used for the characterisation of the final products. --> Abbreviations: NMR: Nuclear Magnetic Resonance GPC-SEC: Gel permeation chromatography-size exclusion chromatography MALDI-ToF-MS: Matrix-Assisted Laser Desorption/Ionization-Time Of Flight (MALDI-TOF) mass spectrometry (MS) SAXS: small-angle x-ray scattering TEM: transmission electron microscopy DSC: differential scanning calorimetry ODT: order-disorder transition SCFT: self-consistent mean-field-theory RDRP: reversible-deactivation radical polymerization BCP: block copolymer RAFT: reversible addition-fragmentation chain transfer polymerization ATRP: atom-transfer radical polymerization BCO: block co-oligomers PTFE: poly(tetrafluoroethene) PFOBiB: perflurooctyl bromoisobutyrate DP: degree of polymerization EBiB: 2-bromoisobutyryl bromide t-BA: tert-butyl acrylate Pt-BA: poly(tert-butyl acrylate) AA: acrylic acid PAA: poly(acrylic acid) TFA: trifluoroacetic acid DMSO: dimethyl sulfoxide THF: tetrahydrofuran DMF: dimethylformamide SVA: solvent vapour annealing TA: thermal annealing F13-Pt-BAn: PFOBiB-initiated poly(tert-butyl acrylate) with average degree of polymerisation n F13-PAAn: PFOBiB-initiated poly(acrylic acid) with average degree of polymerisation n EBiB-PAAn: EBiB-initiated poly(acrylic acid) with average degree of polymerisation n LAM: lamellar HEX: hexagonal packed cylinders --> Software needed to open files according to technique used: for NMR files: ACD-LABS for MALDI-ToF files: Excel, Bruker Data Analysis for GPC files: Agilent GPC for SAXS: EDF Viewer (Foxtrot) for DSC: Excel for TEM: DigitalMicrograph (GMS 3) --> Protocols, parameters, details of equipment used: Nuclear Magnetic Resonance (1H NMR, 13C NMR): NMR spectra were recorded on Bruker HD-300 MHz, HD-400 MHz spectrometers and a Bruker AV III-500 MHz HD spectrometer using a cryoprobe. Monomer conversion was calculated by comparison of vinyl protons (6.4-5.6 ppm) with (CH3)3 protons (1.45 ppm) of Pt-BA. Gel Permeation Chromatography (GPC): THF - Standard. Agilent Infinity II MDS instrument equipped with differential refractive index (DRI), viscometry (VS), dual angle light scatter (LS) and multiple wavelength UV detectors. The system was equipped with 2 x PLgel Mixed C columns (300 x 7.5 mm) and a PLgel 5 µm guard column. The eluent is THF with 2 % TEA (triethylamine) and 0.01 % BHT (butylated hydroxytoluene) additives. Samples were run at 1ml/min at 30’C. Poly(methyl methacrylate) and polystyrene standards (Agilent EasyVials) were used for calibration. Analyte samples were filtered through a GVHP membrane with 0.22 ?m pore size before injection. Respectively, experimental molar mass (Mn,SEC) and dispersity (?) values of synthesized polymers were determined by conventional calibration using Agilent GPC/SEC software. THF - OligoPore. Agilent Infinity II MDS instrument equipped with differential refractive index (DRI) and a 220 nm wavelength UV detector. The system was equipped with an OligoPore column (300 x 7.5 mm) and a PLgel 5 µm guard column. The eluent is THF with no additives. Samples were run at 1ml/min at 30’C. Methyl methacrylate oligomers were used for calibration. Analyte samples were filtered through a GVHP membrane with 0.22 ?m pore size before injection. Respectively, experimental molar mass (Mn,SEC) and dispersity (?) values of synthesized polymers were determined by conventional calibration using Agilent GPC/SEC software.Matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS): Samples for MALDI ToF analysis were dissolved at 10 mg/ml in THF with 1 mg/ml of sodium iodide. 10 µl of this sample mixture was then mixed with 10 µl matrix solution of 40 mg/ml trans-2-[3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) in THF and 1mg/ml of sodium iodide. 0.5 µl of the resulting solution was then spotted on a 384 ground steel multi target plate, using a dried droplet methodology. The dried crystal structure was then analysed using a Bruker autoflex, equipped with a 337 nm N2 laser, operating in reflectron positive mode with an ion source voltage of 19 kV. Data analysis was then carried out on Bruker fleXanalysis and mMass. Small-angle x-ray scattering (SAXS): Small-angle X-ray scattering (SAXS) measurements were made using a Xenocs Xeuss 2.0 equipped with a micro-focus Cu K? source collimated with Scatterless slits. The scattering was measured using a Pilatus 300k detector with a pixel size of 0.172 mm x 0.172 mm. The detector was translated vertically and the images combined to form a virtual detector with double the number of pixels. The distance between the detector and the sample was calibrated using silver behenate (AgC22H43O2), giving a value of 0.339(5) m. The magnitude of the scattering vector (q) is given by?q=4??sin??/??, where?2??is the angle between the incident and scattered X-rays and???is the wavelength of the incident X-rays. This gave a?q?range for the detector of 0.035 Å-1?to 1.66 Å-1. A Pilatus 100k was also used to measure the wider-angle scattering response. This detector was static at an angle of 36° to the beam direction and at a distance of 0.162(2) m. Giving a q range for the detector of to 1.31 Å-1?to 3.27 Å-1. The samples were mounted between two sticky Kapton windows. A radial integration as function of q was performed on the 2D scattering profile and the resulting data corrected for the absorption and background from the sample holder. The wider-angle data were rescaled to match the scale of the SAXS measurements. Differential scanning calorimetry (DSC): Mettler-Toledo DSC1 instrument with autosampler. Samples were cooled with liquid nitrogen and heated at a rate of 10 °C/min from -30 to 180 °C. Transmission electron microscopy (TEM): TEM micrographs were obtained using a JEOL JEM-2100 transmission electron microscope at an accelerating voltage of 200 kV. The samples for TEM were prepared by dropcasting 7 ?L of the diluted solution (1-3 mg of sample dissolved in 1 mL of methanol) onto graphene oxide-copper grids supplied by EM Resolutions and were left to dry at room temperature for 30 minutes. For the solvent annealing, the dropcasted grids were placed under a MeOH-rich environment for 24 hours. For the thermal annealing, the dropcasted grids were first left to dry at ambient temperature and then placed in an oven for 24 hours at 120 degrees.