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Phosphonium Saltss Reaction Lab Report

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Synthesis of tetrakis (pyrrolidino) phosphonium tetrafluoroborate (Py4P1+BF4-), tetrakis (piperidino) phosphonium tetrafluoroborate (Pi4P1+BF4-), and tetrakis (morpholino) phosphonium tetrafluoroborate (Mo4P1+BF4-).
Stoichiometric pyrrolidino, piperidino, and morpholino were reacted with PCl5 in absolute CH2Cl2 or chlorobenzene at various temperatures. After the completion of the reactions, NH4BF4/H2O was added at room temperature. The resulting products were washed with solvents, and the white solids thus obtained were isolated by filtration and dried in vacuum. The reactions with three phosphonium salts are shown by Equations (2), (3), and (4). 1H-NMR (Py4P1+BF4-, 400MHz, CDCl3, 30 °C, TMS): δ = 1.94 ppm (m. 16H. NCH2CH2), 3.21 ppm (m, …show more content…

1H-NMR (P5+BF4-, 400MHz, CDCl3, 30 °C, TMS): δ = 2.60 ppm (m, 72H, CH3). (Figure S6); IR (KBr): 2934 (s), 2819 (s), 1472 (m), 1397 (w), 1301 (w), 1219 (m), 1103 (vs), 1058 (vs), 978 (vs), 745 cm-1 (w) (Figure S1); MS (ESI) m/z: calcd for C24H72N16P5Cl, 774.4497; found, 774.3795.
2.2.4 Synthesis of phosphonium methanol (P+CH3O-)
Phosphonium tetrafluoroboron salts were dissolved in anhydrous methanol and stirred at room temperature. Stoichiometric potassium methoxide was added to the flask, and the precipitated KBF4 was filtered off after reaction for 2 h, and the methanolic solution was reserved.
2.3 Ring-opening polymerization of PO
Glycerol was partially deprotonated with the P+CH3O- by distilling off methanol under vacuum at 70 °C for 1 h in a sealed glass vessel (50 mL), and dried overnight at 110 °C). Stoichiometric PO was pushed into a vessel set in a pre-heated oil-bath for polymerization, cooled to room temperature, and the residual monomer was removed by evaporation when the polymerizations were finished. Excess methanol and cation exchange resin (Amberlite IR-120) were added to the crude products and stirred at 25 °C for 1 h. Purified PPOs were obtained after filtration and removal of methanol, and characterized by NMR (1H and 13C) spectroscopy and gel permeation chromatography …show more content…

The catalysts were mixed with a KBr salt pellet. FTIR spectra were generated from 32 scans in the wavenumber range 4000–400 cm-1 at a resolution of 4 cm-1.
2.4.2 NMR
1H NMR and 13C NMR spectra were recorded using a Bruker Biospin AG, Magnet System 400 MHz/54 mm spectrometers at 25 °C, using chloroform-d (CDCl3) as the solvent and trimethylsilane as the internal standard.
2.4.3 Gel Permeation Chromatography (GPC)
GPC Measurements were performed using a Waters 1515 Isocratic HPLC using tetrahydrofuran (THF) as an eluent at 35 °C, at a flow rate of 1.0 mL/min. The polymers were dissolved in THF at a concentration of 6 mg/mL. The system was calibrated using a series of monodisperse linear PPO standards with molecular weights in the range 200–12000 g/mol.
2.4.4 Electrospray ionization mass spectrometry (ESI-MS)
ESI-MS Measurements were performed using a Micromass LCTTM Liquid Chromatography/Time-of-Flight Mass Spectrometer equipped with a Waters 600 Liquid Chromatography System.
2.4.5 The degree of unsaturation (C=C)
The degree of unsaturation was calculated by 1H-NMR. 1H-NMR (PPO, 400 MHz, CDCl3, TMS): δ = 1.12 ppm (m. CH3), 3.20–3.80 ppm (CH2, CH), 3.13 ppm (CH2CHOH), 3.90 ppm (CH2CHOH), 5.14 ppm (CH2=CH-CH2), 5.27 ppm (CH2=CH-CH2), 5.87 ppm (CH2=CH-CH2) (Figure

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