Synthesis of some organotin monomers and copolymerisation with acrylic monomers

• Main Author: Al-Feir, Saud M. H.
• Published: Loughborough University 1996
• Subjects: 547; Organic chemistry
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.360837

The aim of this thesis was to synthesise new organotin monomers based on Nsubstituted acrylamide and methacrylamide and on acrylic acid and methacrylic acid esters with pendant hydrolysable organotin moieties and to study their copolymerisation with methyl acrylate (MA), butyl acrylate (BA) and methyl methacrylate (MMA). A specific objective was to obtain suitable macromolecular chains, to which the organotin moieties could be attached at some distance from the main backbone. The new organotin monomers which were synthesised are: m-acrylamidotri-n-butyltin benzoate (m-AATBTB), p-acrylamidotri-n-butyltin benzoate (p-AATBTB), m-methacrylamidotri-n-butyltin benzoate (mMAATBTB), p-methacrylamidotri-n-butyltin benzoate (p-MAATBTB), 0- acryloyloxytri-n-butyltin benzoate (o-AOTBTB) and o-methacryloyloxytri-nbutyltin benzoate (o-MAOTBTBO). These were prepared by the reaction of bis(tri-n-butyltin) oxide (TBTO) with the corresponding acrylamide or acryloyloxy benzoic acid which were prepared by the reaction of aminobenzoic acid derivatives or salicylic acid with either acryloyl chloride or acrylic anhydride. These organotin monomers were polymerised in dimethylformamide (DMF) solution with azobisisobutyronitrile (AIBN) as initiator. Binary copolymerisation experiments were performed by solution polymerisation in DMF solution with AIBN as initiator. The copolymer composition in each case was determined from tin analysis. Since the properties of these organotin polymers are related to the distribution of monomer units, it is of great interest to determine the actual monomer reactivity ratios which control the sequence length distribution. Monomer reactivity ratios were calculated by the KelenTudos method. All of these organotin polymers and copolymers were characterised by Nuclear magnetic resonance spectroscopy (NMR) and Fourier Transform infrared spectroscopy (FTIR) methods, gel permeation chromatograghy (GPC) and dynamic mechanical thermal analysis (DMTA).