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Synthesis and Characterization of Aliphatic-Aromatic Polyesters

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Synthesis and Characterization of Aliphatic-Aromatic Polyesters SYNTHESIS AND CHARACTERIZATION OF ALIPHATIC-AROMATIC POLYESTERS Thesis submitted to the UNIVERSITY OF PUNE for the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY by T. E. Sandhya Division of Polymer Chemistry National Chemical Laboratory PUNE – 411 008 INDIA November 2003 To Shankar Acknowledgements This doctoral research could not have been conducted were it not for several people who offered advice, inspiration and encouragement. To my advisor, Dr. S. Sivaram: your clever insights and extensive knowledge of polymer chemistry coupled with your concern for people and promotion of others, has inspired me to persevere through difficult stretches of research. I am certain that the guidance and training you have provided me has laid the foundation for future success. I would like to thank council of scientific and industrial research, New Delhi for the award of fellowship and Director, NCL for allowing me to carry out this investigation in this prestigious research laboratory. I take this opportunity to express my deep sense of gratitude to Dr. C. Ramesh for his extreme cooperation, help and patience. His valuable suggestions went a long way in giving appropriate dimension to this work. I sincerely thank Dr. C. V. Avadhani, who extended his help and support whenever I needed and Dr. P. P. Wadgaonkar for valuable discussions and references. With much pleasure I thank my friends Nirmala, Ramanathan, Soumen, Shrilakshmi, Viji, Sulatha, Bindu, Uday and Sachin for their valuable and timely help. Many thanks go to all my colleagues and scientists in polymer chemistry division for their cooperation. I thank the members of central NMR facility, elemental analysis, SIL, SMIS, glass blowing, stores, workshop and administrative group for their technical support. I am blessed with very loving and caring parents in law and sisters in law. I am grateful to them for their sincere encouragement and love, especially to my mother in law for boosting my enthusiasm all the time. Special gratitude goes to my parents for their support and commitment to help me succeed. The highest recognition goes to my mother, whose hopeful disposition, timely encouragement and deep faith in her God has motivated me to persevere and properly prioritize my life. To my father, who instilled in me desire to learn, strong work ethic and the value of common sense. I should not fail to mention my sister Vidhya and brother Dnyaneshwar for being with me and giving moral support all the time. And this is to my love, Shankar: your lavish support, immense love and patience beyond limits have brought this thesis to a reality. Your energy and exuberance always lifted me higher. Your smile brightens my every day. (T. E. Sandhya) ABSTRACT This thesis presents the synthesis, characterization and crystallization behavior of copolyesters of dimethyl terephthalate and 1,4-butanediol with various cycloaliphatic diols and diesters. Aliphatic polyesters containing cycloaliphatic diols and diesters were also synthesized and characterized. A series of poly(butylene terephthalate-co-1,4-cyclohexylene dimethylene terephthalate) (P(BT-co-CT)) and poly(butylene terephthalate-co-1,4- cyclohexane dicarboxylate) (P(BT-co-BCD)) copolymers with various CT and BCD contents were synthesized by melt condensation. The NMR spectroscopic analysis indicates that the copolymers are statistically random, irrespective of the composition. The thermal analysis and XRD studies show that these copolymers could crystallize in all compositions. The poly(BT- co-CT) copolymers exhibited typical eutectic behavior in melting and crystallization and the eutectic composition is PBT75CT25 indicating iso-dimorphic cocrystallization behavior. On the other hand, poly(BT-co-BCD) copolyesters showed isomorphic crystallization but did not show eutectic behavior in melting and crystallization. The glass transition temperature showed linear dependency on composition in these copolymers. The crystallization behavior and crystallization kinetics of the commercial PCCD was studied by DSC and compared with PBT and PCT. PCT is a rapidly crystallizing polymer like PBT and has short crystallization half time (less than 0.5 minute over wide range of temperature from 110 to 275°C). PCCD, on the other hand, crystallizes slowly and shows unique minimum crystallization half time at two different temperatures. Cyclopentane ring containing monomers, 1,3-bis(hydroxymethyl) cyclopentane and dimethyl-1,3-cyclopentane dicarboxylate were synthesized. Copolyesters of dimethyl terephthalate and 1,4-butanediol containing 1,3-bis(hydroxymethyl) cyclopentane (CPDM) and dimethyl-1,3-cyclopentane dicarboxylate (CPDE), namely, poly (butylene terephthalate-co-1,3-cyclopentylene dimethylene terephthalate) [P(BT-co-CPDT)] and poly (butylene terephthalate-co-butylene cyclopentane dicarboxylate) [P(BT-co-BCP)] i were synthesized by melt condensation. The thermal analysis and XRD studies show that poly(BT-co-CPDT) copolymers could crystallize in all compositions. The poly(BT- co-CPDT) copolymers exhibit typical eutectic behavior in melting and crystallization and iso-dimorphic cocrystallization. The homopolyester of 1,3-bis (hydroxy methyl) cyclopentane and DMT (PCPDT) was found to be a semicrystalline polyester. PCPDT has lower crystallization rate compared to PBT and shows well defined banded spherulitic morphology. The homopolyester of dimethyl-1,3-cyclopentane dicarboxylate with DMT (PBCP) was found to be an amorphous polyester. The poly(BT-co-BCP) copolyesters containing upto 50 % BCP component was found to be semicrystalline. In the composition range where the copolyesters crystallized, the samples show isomorphic crystallization but do not show eutectic behaviour in melting and crystallization. The glass transition temperature exhibits linear dependency on composition in these copolymers. Aliphatic polyesters, poly(cyclohexanedimethylene cyclohexanedicarboxylate) (PCCD) and poly (cyclopentane dimethylene cyclopentane dicarboyxlate) (PCPCPD) were synthesized and characterized. The PCCD synthesized contains 67 % axial,equatorial- cyclohexane dicarboxylate and is an amorphous polymer. PCPCPD was found to be an amorphous rubbery polymer at room temperature with a Tg well below room temperautre. A series of poly(butylene terephthalate-co-2,3-norbornane dimethylene terephthalate) (P(BT-co-NBDT)) and poly (butylene terephthalate-co-2,3-norbornane dicarboyxlate) (P(BT-co-BNB)) copolymers with various NBT and BNB contents were synthesized by melt condensation. The NMR spectroscopic analysis indicates that the coploymers are random. The thermal analysis and XRD studies shows that the PNBDT is an amorphous polyester with a Tg of 113°C. The poly(BT-co-NBDT) copolyesters could crystallize in compositions upto 20 % NBDT content, while the composition having 50 % NBDT is amorphous. On the other hand, PBNB was found to be an amorphous polyester with a Tg of 15°C. The poly(BT-co-BNB) copolyesters show isomorphic crystallization but did not show eutectic behaviour in melting and crystallization. ii Copolyesters of TMCBD/BD containing, dimethyl terephthalate, 1,4-cyclohexane dicarboxylate, 1,3-cyclopentane dicarboxylate and 2,3-norbornane dicarboxylate are synthesized and found to be amorphous. The incorporation of the rigid cyclobutane diol o boosts the Tg by about ~ 45 C compared to the corresponding homopolymers. iii GLOSSARY BD 1,4-butanediol BHCT Bis(hydroxymethyl cyclohexane) terephthalte BT Butylene terephthalate unit BHBT Bishydroxybutyl terephthalte B Degree of randomness BCD Butylene cyclohexane dicarboxylate unit BPA Bisphenol-A CHDM 1,4-cyclohexane dimethanol CHDA 1,4-cyclohexane dicarboxylic acid CT Cyclohexylene dimethylene terephthalate unit CPDE 1,3-cyclopentane dicarboxylate, dimethyl ester CPDM 1,3-cyclopentane dimethanol (1,3-bishydroxymethyl)cyclopentane) CPDT Cyclopentylene dimethylene terephthalate unit DMT Dimethyl terephthalate DMCD Dimethyl-1,4-cyclohexane dicarboxylate DSC Differential scanning calorimetry DMNBDE 2-exo, 3-exo-dimethyl bicyclo[2.2.1]heptane-2-endo,3-endo- dicarboxylic acid dimethyl ester DEG Diethylene glycol DMI Dimethyl isophthalate DMN 2,6-dimethyl naphthalate DMS Dynamic mechanical spectroscopy EG Ethylene glycol GC Gas chromatography ∆Hm Enthalpy of melting ∆Hc Enthalpy of crystallization ∆Hƒ Enthalpy of ∆Hcc Enthalpy of cold crystallization HDT Heat distorsion temperature HBPA Hydrogenated bisphenol-A IDT Intial decomposition temperature IR Infrared IPA Isophthalic acid k Overall rate constant LAH Lithium aluminum hydride LnB Average sequence length of butylene unit LnC Average sequence length of cyclohexylene dimethylene unit LnCD Average sequence length of cyclohexane dicarboyxlate unit LnT Average sequence length of terephthalate unit LCP Liquid crystalline polymer Mn Number average molecular weight Mw Weight average molecular weight NBDE dimethyl bicyclo[2.2.1]heptane 2-exo,3-endo dicarboxylate (dimethyl 2-exo,3-endo norbornane dicarboxylate ) iv NBDM 2-endo, 3-endo bis(hydroxymethyl) bicyclo [2.2.1]heptane (2-endo, 3-endo norbornane dimethanol) NMR Nuclear magnetic resonance N2 Nitrogen gas N Avrami exponent NPG Neopentyl glycol NDA Nadic anhydride PBT Poly(butylene terephthalate) PCT Poly(cyclohexylene dimethylene terephthalate) PET Poly(ethylene terephthalate) PCCD Poly(cyclohexylene dimethylene cyclohexane dicarboxylate) PBCD Poly(butylene-1,4-cyclohexane dicarboxylate) PCPDT poly (1,3-cyclopentane dimethylene terephthalate) PNBDT poly(2,3-norbornane dimethylene terephthalate) PBNB poly (butylene-2,3-norbornane dicarboxylate)
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