Synthesis and Characterization of Cycloaliphatic and Aromatic Polyester/Poly(dimethylsiloxane) Segmented Copolymers
Mecham, Jeffrey Brent
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Linear thermoplastic polyesters are commonly used in high volume applications such as food containers, films and textile fibers. The physical and mechanical properties of these materials are well documented and are a function of chemical structure and morphology (e.g. semi-crystalline, amorphous, etc.). Polyesters, as are many organic polymers, are quite flammable. Polydimethylsiloxane homopolymer exhibits low mechanical strength and, even at high molecular weight, exists as a viscous fluid rubbery gum due to its low glass transition temperature of approximately -123Â°C. However, one of the many attractive properties of this polymer is its relatively low flammability and if properly designed, organic â sand-likeâ silicates are produced in oxidizing atmospheres at elevated temperatures (e.g. 500-700Â°C). This thesis discusses the synthesis and characterization of novel, high molecular weight cycloaliphatic and aromatic polyester/ poly(dimethylsiloxane) segmented copolymers. The cycloaliphatic copolymers were synthesized via a melt process using a high trans content 1,4 dimethylcyclohexanedicarboxylate, and 1,4 butanediol or cyclohexanedimethanol, while the partially aromatic systems were synthesized using dimethyl terephthalate and butanediol. Primary and secondary aminopropyl terminated poly(dimethylsiloxane) oligomers of controlled molecular weight were endcapped with excess diester to form an amide linked diester terminated oligomer. The latter was then incorporated into the copolymer via melt transesterification to afford a multiphase segmented copolymer. Selected compositions showed enhanced ductility and hydrophobic surface modification. The polysiloxane segment was effeciently incorporated into the copolymers and was unaffected by the transesterification catalyst under typical reaction conditions. The homopolymers and copolymers were characterized by solution, thermal, and mechanical, and surface techniques. The segmented copolymers were demonstrated to be microphase separated as determined by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and transmission electron microscopy. The surface of the copolymers was enriched with the polysiloxane segment as evidenced by contact angle analysis. Thermal gravimetric analysis of the segmented copolymers containing identical amounts of PDMS, but varying in the primary or secondary nature of their amide linkages, exhibited quantitatively identical char yields and weight loss behavior. The segmented copolymers exhibited char yields in air superior to those of their respective homopolymers. Additionally, aromatic poly(tetramethyleneoxide) (PTMO) based polyether/polyester segmented copolymers were modified with poly(dimethylsiloxane). DMA revealed an apparent shift (higher Tg) of the PTMO segment reflecting an increase in phase mixing with the â hardâ polyester segment, possibly induced by the hydrophobic PDMS phase.
- Masters Theses