Synthesis and solid-state NMR structural characterization of some functionalized polysiloxanes

Polysiloxane-immobilized propylamine, diethylpropylamine and trimethylpropylammonium systems, and some other types of ligand systems, have been prepared. Polysiloxane-immobilized amine and trimethylpropylammonium chloride materials were made through hydrolytic condensation of Si(OEt)(4) and (EtO)(3)Si(CH2)(3)X, with X=-NH2 or -N+(CH3Cl-. The polysiloxane-immobilized diethylpropylamine ligand system was prepared by the reaction between the polysiloxane-immobilized 3-chloropropyl system and diethylamine. Polysiloxanes carrying the -CH(2)CO(2)Me group were made by the reaction of methylchloroacetate with polysiloxane-immobilized amine or thiol ligand systems, S-(CH2)(3)X (where X = -NH2 or -SH; and S represents the polysiloxane backbone). Polysiloxane-immobilized glycinate and iminodiacetate systems were made by the reactions of sodium glycinate or disodium iminodiacetate with the polysiloxane-immobilized 3-chloropropyl system. Solid-state C-13 and Si-29 NMR spectroscopy, based on cross polarization (CP) and magic-angle spinning (MAS) techniques, were employed. C-13 NMR results determined that, in the above-mentioned glycinate and iminodiacetate substitution reactions, the acetate groups of glycinate and iminodiacetate systems serve as the reaction site for displacement of the chloride in the polysiloxane-immobilized 3-chloropropyl system.