@phdthesis{Imranulhaq2008, author = {Imran ul-haq, Muhammad}, title = {Synthesis of fluorinated polymers in supercritical carbon dioxide (scCO₂)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-19868}, school = {Universit{\"a}t Potsdam}, year = {2008}, abstract = {For the first time stabilizer-free vinylidene fluoride (VDF) polymerizations were carried out in homogeneous phase with supercritical CO₂. Polymerizations were carried out at 140°C, 1500 bar and were initiated with di-tert-butyl peroxide (DTBP). In-line FT-NIR (Fourier Transform- Near Infrared) spectroscopy showed that complete monomer conversion may be obtained. Molecular weights were determined via size-exclusion chromatography (SEC) and polymer end group analysis by 1H-NMR spectroscopy. The number average molecular weights were below 104 g∙mol-1 and polydispersities ranged from 3.1 to 5.7 depending on DTBP and VDF concentration. To allow for isothermal reactions high CO₂ contents ranging from 61 to 83 wt.\% were used. The high-temperature, high-pressure conditions were required for homogeneous phase polymerization. These conditions did not alter the amount of defects in VDF chaining. Scanning electron microscopy (SEM) indicated that regular stack-type particles were obtained upon expansion of the homogeneous polymerization mixture. To reduce the required amount of initiator, further VDF polymerizations using chain transfer agents (CTAs) to control molecular weights were carried out in homogeneous phase with supercritical carbon dioxide (scCO₂) at 120 °C and 1500 bar. Using perfluorinated hexyl iodide as CTA, polymers of low polydispersity ranging from 1.5 to 1.2 at the highest iodide concentration of 0.25 mol·L-1 were obtained. Electrospray ionization- mass spectroscopy (ESI-MS) indicates the absence of initiator derived end groups, supporting livingness of the system. The "livingness" is based on the labile C-I bond. However, due to the weakness of the C-I bond perfluorinated hexyl iodide also contributes to initiation. To allow for kinetic analyses of VDF polymerizations the CTA should not contribute to initiation. Therefore, additional CTAs were applied: BrCCl3, C6F13Br and C6F13H. It was found that C6F13H does not contribute to initiation. At 120°C and 1500 bar kp/kt0.5~ 0.64 (L·mol-1·s-1)0.5 was derived. The chain transfer constant (CT) at 120°C has been determined to be 8·10-1, 9·10-2 and 2·10-4 for C6F13I, C6F13Br and C6F13H, respectively. These CT values are associated with the bond energy of the C-X bond. Moreover, the labile C-I bond allows for functionalization of the polymer to triazole end groups applying click reactions. After substitution of the iodide end group by an azide group 1,3 dipolar cycloadditions with alkynes yield polymers with 1,2,3 triazole end groups. Using symmetrical alkynes the reactions may be carried out in the absence of any catalyst. This end-functionalized poly (vinylidene fluoride) (PVDF) has higher thermal stability as compared to the normal PVDF. PVDF samples from homogeneous phase polymerizations in supercritical CO₂ and subsequent expansion to ambient conditions were analyzed with respect to polymer end groups, crystallinity, type of polymorphs and morphology. Upon expansion the polymer was obtained as white powder. Scanning electron microscopy (SEM) showed that DTBP derived polymer end groups led to stack-type particles whereas sponge- or rose-type particles were obtained in case of CTA fragments as end groups. Fourier-Transform Infrared spectroscopy and wide angle X-ray diffraction indicated that the type of polymorph, α or β crystal phase was significantly affected by the type of end group. The content of β-phase material, which is responsible for piezoelectricity of PVDF, is the highest for polymer with DTBP-derived end groups. In addition, the crystallinity of the material, as determined via differential scanning calorimetry is affected by the end groups and polymer molecular weights. For example, crystallinity ranges from around 26 \% for DTBP-derived end groups to a maximum of 62 \% for end groups originating from perfluorinated hexyl iodide for polymers with Mn ~2200 g·mol-1. Expansion of the homogeneous polymerization mixture results in particle formation by a non-optimized RESS (Rapid Expansion from Supercritical Solution) process. Thus, it was tested how polymer end groups affect the particles size distribution obtained from RESS process under controlled conditions (T = 50°C and P = 200 bar). In all RESS experiments, small primary PVDF with diameters less than 100 nm without the use of liquid solvents, surfactants, or other additives were produced. A strong correlation between particle size and particle size distribution with polymer end groups and molecular weight of the original material was observed. The smallest particles were found for RESS of PVDF with Mn~ 4000 g·mol-1 and PFHI (C6F13I) - derived end groups.}, language = {en} }