--> Project: Heterotelechelic homopolymers mimicking high – ultralow N block copolymers with sub-2 nm domain size --> Folder Structure: The files are organised by technique used for the characterisation of the final products. --> Software needed to open files according to technique used: for NMR files: ACD-LABS for MALDI-ToF files: Origin for GPC: Origin for SAXS: Origin for DSC: Origin --> 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 equipped with a cryoprobe. Monomer conversion was calculated by comparison of vinyl protons (6.4-5.6 ppm) with (CH3)3 protons (1.45 ppm) of PtBA. Gel Permeation Chromatography (GPC): THF - Standard. Agilent Infinity II MDS instrument equipped with differential refractive index (DRI). 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 used was THF with 2 % TEA (triethylamine) and 0.01 % BHT (butylated hydroxytoluene) additives. Samples were run at 1 ml/min at 30°C. Narrow molecular weight poly(methyl methacrylate) (11 narrow standards between 2210000-1010 Da) and polystyrene standards (12 narrow standards between 364000-160 Da (Agilent EasiVials) were used for calibration. Analyte samples were filtered through a GVHP membrane with 0.22 μm pore size before injection. Respectively, experimental molar mass (Mn) and dispersity (Đ) values of synthesised polymers were determined by conventional calibration using Agilent GPC/SEC software. (MALDI-ToF-MS): Samples (of lower molecular weight) 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 1 mg/ml of sodium iodide. Samples (of higher molecular weight) for MALDI ToF analysis were dissolved at 10 mg/ml in H2O 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 2,5-Dihydroxybenzoic acid (DHB) in MeOH and 1 mg/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): Single data acquisition measurements. X-ray scattering measurements were made using a Xenocs Xeuss 2.0 equipped with a micro-focus Cu Kα source collimated with Scatterless slits. For static measurements, samples were mounted between two sticky Kapton windows. Small-angle X-ray scattering (SAXS) 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 to obtain data over a wider q range. The magnitude of the scattering vector (q) is given by q = 4𝜋sin𝜃/𝜆, where 2𝜃 is the angle between the incident and scattered X-rays and λ is the wavelength of the incident X-rays. The distance between the detector and the sample was calibrated using silver behenate (AgC22H43O2), giving a value of 0.339(5) m, corresponding to a q range of 0.035 Å-1 to 1.66 Å 1. Radial integration as a function of q was performed on the 2D scattering profiles and the resulting data corrected for the absorption and background from the sample holder. Time-resolved SAXS during thermal annealing measurements. These experiments were carried out in a similar way to the single data acquisition measurements, with a Linkam HFSX 350 being used to control the temperature of samples mounted between Kapton sheets. Samples were heated and cooled at a rate of 0.5 °C/min while making 1 min data collections. After every 5 measurements the transmitted intensity was measured for making corrections. Liquid initiator measurements. These were carried out in a similar way to the single data acquisition measurements but the samples were mounted in 1 mm diameter borosilicate glass capillaries instead. The Kapton peak is present due to the Kapton windows used in the main SAXS chamber. These windows are necessary to allow air into the chamber for liquid samples. Differential scanning calorimetry (DSC): Data for F13-PAAm polymers were obtained using a Mettler-Toledo DSC1 with autosampler under nitrogen, samples were heated and cooled between 25-180 oC at 10 oC per minute. Heating cycles were repeated 3 times. Data for F17-PAAm and F21-PAAm polymers were obtained using PEDSC6000 with intracooler, samples were heated and cooled between 0-200 oC at 10 oC per minute. Heating cycles were repeated 3 times.