Synthesis and Physical Properties of Polyester Amides Derived from Lipid-Based Components

1 Synthesis and Physical Properties of Polyester Amides Derived from Lipid-Based Components By: Jiaqing Zuo Trent Biomaterials Research Group March 2011 2 Outline Introduction of polyester amide (PEA)  What is polyester amide  Applications Advantage of Lipid-based components Previous Examples of Lipid-based PEA Objectives and Results Conclusions 3 Introduction  What is polyester amide (PEA) Boc H N COOH Boc H N O O O O H N Boc O OOO TFA H N O O O O H N O OOO Cl Cl O O H 2 N O O O O NH 2 O OOO * O * O n HO O O OH O O 1 2 Ester linkage Amide linkage Ester linkage: Biodegradability Amide linkage: Thermal Stability, Mechanical Strength 4  Applications Biomedical applications:  Stent-coatings for drug delivery  Absorbable surgical materials Material requirements:  Biodegradable  Good processing property  Safely metabolized by human bodies References: 1. Lee, S.H., et al., Coronary Artery Disease, 2002. 13(4): p. 237-241. 2. Legashvili, I., et al., Journal of Biomaterials Science-Polymer Edition, 2007. 18(6): p. 673-685. 3. Guo, K. and C.C. Chu, Journal of Polymer Science Part a-Polymer Chemistry, 2005. 43(17): p. 3932-3944. 5 Advantage of Lipid-based components Functional groups:  Carboxylic group  Double bonds Advantages:  Economically friendly  Environmentally friendly  Potentially have good performance as petroleum based materials References: 1. Hojabri, L., X.H. Kong, and S.S. Narine,. Biomacromolecules, 2009. 10(4): p. 884-891. 2. Williams, C.K. and M.A. Hillmyer,. Polymer Reviews, 2008. 48(1): p. 1-10. 6 Previous Examples of Lipid-based PEA PEA derived from: Pongamia glabra oil Linseed oil Disadvantages:  Not all building blocks are from sustainable materials  Not suitable for biomedical applications References: 1. Ahmad, S., S.M. Ashraf, and F. Zafar,. Journal of Applied Polymer Science, 2007. 104(2): p. 1143-1148. 2. Zafar, F., et al.,. Journal of Applied Polymer Science, 2005. 97(5): p. 1818-1824. 3. Ahmad, S., et al.,. Progress in Organic Coatings, 2003. 47(2): p. 95-102. O O O O R R O R O HN OH OH + N OH OH R O OH O HO O NaOCH 3 Diethanolamine 7 Objectives 1. Synthesis of PEAs with different ester/amide ratios PEA (I) with ester: amide= 1:1 PEA (II) with ester: amide= 2:1 PEA (III) with ester: amide= 3:1 8 Hypotheses: 1. The increase of ester to amide ratios in the PEA structure will result in a decrease of thermal stability 2. The increase of ester to amide ratio in PEA structure will decrease the glass transition temperature 3. The increase of ester to amide ratio in PEA will result in increased elasticity 4. The increase of ester to amide ratio in PEA structure will diminish the mechanical strength of the polymer 9 Step 1: Synthesis of different diols from oleic acid 1, 9-Nonanediol Synthesis of the PEA 10 Di-ester diol Tetra-ester diol Step 1: Synthesis of different diols from oleic acid [...]... 3.64 30  Comparison of lipid-based polyester amides Tg (oC) Tm (oC) Tensile strength Elongation 3 87.8 19.6MPa 12% 300 -20 77.4 10.2MPa 14.3% 300 PEAs in our research TD (oC) 300 Sources and Structures -34 76.0 8.5MPa 12% 163-220 (5%) 155 Features Derived from oleic acid Linseed oil, diethanolamine DEA Anticorrosive coatings and diacid From fatty acids Pongamia glabra oil, DEA and diacid 275 (10%)... synthesized from lipid-based components  The PEAs were fully characterized  Functionality of the PEAs were investigated from a structural perspective  PEA’s had superior properties to all other lipid-based PEAs  PEA’s had comparable and sometimes superior properties to petroleum-based PEAs Hypothesis #1: The increase of ester to amide ratio in the PEA structure resulted in a decrease of thermal stability... applications and adipic acid Gallic acid, amino acid 249-305 (5%) 141-168 180 Highly branched, aromatic 120 Potental antibacterial activities Castor/soyabean oil, DEA, adipic acid and 260 Zn(OH)2 31  Comparison with petroleum-based polyester amides Sources and Structures From petroleum Cyclohexyl diol, diacyl chloride, cyclohexyl sebacamide Di-p-nitrophenyl sebacate and ptoluenesulfonic acid salt of Lphenylalanine... Copolymer Random combination of polyester and nylon BAK 1095 Caprolactam (Nylon 6) Butanediol, Adipic acid BAK 2195 Nylon 6,6; Diethylene glycol Butanediol, Adipic acid 20 80, 87 Glucitol(diol), amino acid, aliphatic dicarboxylic acid -45 to -5 Around 380 Tensile strength (MPa) Elongation (%) 83 to140 -15 to -6 32 Conclusions  Three PEAs with different ratios of ester and amide linkages were synthesized from. .. of thermal stability a The increase of ester to amide ratio did not impact dramatically the thermal degradation of the PEAs b The increase of ester to amide ratio decreased the thermal stability at the melting behaviour level 34 Hypothesis #2: The increase of ester to amide ratio in PEA structure decreased dramatically the glass transition temperature a The increase of ester to amide ratio in PEA structure...Characterization of the diols  1H-NMR spectra 1, 9-Nonanediol Di-ester diol Tetra-ester diol 11 Step 2: Polyester amide preparation PEA 12  Characterization of PEAs  FT-IR spectra of PEAs N-H stretching vibration: 3200–3500 cm-1 C-H stretching vibration: 2850-3000 cm-1 C=O stretching vibration: 1700–1740... transition temperature b This is an improvement as materials with lower Tg can be used flexible in a wider range 35 Hypothesis #3: The increase of ester to amide ratio in PEA resulted in an increased elasticity From the result of tan Delta, the elasticity of PEA increased when ester to amide ratio increased at room temperature 36 ... Crystallization Temperature 20 3) Dynamic Mechanical Analysis (DMA) • Viscoelastic properties • Measuring glass transition temperature 21  DMA Results Storage Modulus at 37 oC 22  DMA Results Tan  E / E PEA (I) PEA (II) PEA (III) Tg (oC) (DMA) 17.9 -1.6 -15.0 Tg (oC) (DSC) 3.4 -20.0 -34.1 Tg (DMA) is reported from the peak value of tan δ 23  Tg (DMA) versus Structures 24 4) Tensile analysis • Ultimate... 1,6-hexanediamine, sebacic acid octadecanedioic acid, and εcaprohctone Different aromatic diols, diacids and 4-acetamidophenol (AP) TD (oC) Tg (oC) Tm (oC) 250 -36 to -7 68 to 97 30 109.2 231 to 391 -24 to 48 Copolymer 950 3.18GPa, 3.94GPa