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Influence of the Processes Parameters on the Properties of The ...

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Chapter 1.<br />

Polylactide Based Bio-Materials<br />

or lactic acid) are linked toge<str<strong>on</strong>g>the</str<strong>on</strong>g>r in PLGA by ester linkages, thus resulting in linear, aliphatic polyester as a<br />

product [Middlet<strong>on</strong> and Tipt<strong>on</strong>, 1998]. Using <str<strong>on</strong>g>the</str<strong>on</strong>g> polyglycolide and polylactide properties as a starting point,<br />

it is possible to copolymerize <str<strong>on</strong>g>the</str<strong>on</strong>g> two m<strong>on</strong>omers to extend <str<strong>on</strong>g>the</str<strong>on</strong>g> range <str<strong>on</strong>g>of</str<strong>on</strong>g> homopolymer properties.<br />

Copolymers <str<strong>on</strong>g>of</str<strong>on</strong>g> glycolide with both L-lactide and D,L-lactide have been developed for both device and drug<br />

delivery applicati<strong>on</strong>s.<br />

Figure 1.5: Schemaic syn<str<strong>on</strong>g>the</str<strong>on</strong>g>sis <str<strong>on</strong>g>of</str<strong>on</strong>g> poly(lactide-co-glycolide).<br />

[Middlet<strong>on</strong> and Tipt<strong>on</strong>, 1998]<br />

To tailor <str<strong>on</strong>g>the</str<strong>on</strong>g> processability and to enhance biodegradati<strong>on</strong>, <str<strong>on</strong>g>the</str<strong>on</strong>g>se copolymers are fur<str<strong>on</strong>g>the</str<strong>on</strong>g>r modified<br />

by copolymerizing with linear dicarboxylic acids (e.g. adipic acid) and glycol comp<strong>on</strong>ents with more than<br />

four methylene groups (e.g. hexanediol) [Sublett, 1983]. To enhance <str<strong>on</strong>g>the</str<strong>on</strong>g> envir<strong>on</strong>mentally benevolent aspect<br />

<str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g>se materials and to broaden <str<strong>on</strong>g>the</str<strong>on</strong>g> range <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g>ir use, aliphatic-aromatic co-polyesters blended with<br />

cellulose esters have been processed into useful fibres, films and moulded objects [Buchanan et al., 1994,<br />

1995].<br />

2.2.2 <strong>Properties</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> PLGA Copolymers<br />

Physical properties <str<strong>on</strong>g>of</str<strong>on</strong>g> poly(glycolic acid), as well as different PLGAs, are ga<str<strong>on</strong>g>the</str<strong>on</strong>g>red in Table 1.3.<br />

Table 1.3: Main physical properties <str<strong>on</strong>g>of</str<strong>on</strong>g> PGA and several PLGAs.<br />

<strong>Properties</strong> Unit PGA P D,L LGA 50:50 P D,L LGA 75:25 P D,L LGA 85:15<br />

Density ρ gm/cm 3 1.5−1.7 1.3−1.4 1.3 1.25<br />

Tensile strength σ MPa 60−99.7 41.4−55.2 41.4−55.2 45−52<br />

Tensile modulus E GPa 6−7 1−4.3 1.4−4.1 2.0*<br />

Ultimate strain ε % 1.5−20 2−10 2.5−10 −<br />

Specific tensile strength S* Nm/g 40−45.1 30.9−41.2 31.8−42.5 −<br />

Specific tensile modulus E* kNm/g 4−4.5 8−2.1 1.1−2.1 −<br />

Glass transiti<strong>on</strong> temperature T g °C 35−40 45−50 50−55 55−55<br />

Melting point T m °C 225−230 amorphous amorphous amorphous<br />

[Van de Velde and Kiekens, 2002]<br />

Polyglycolide has a glass transiti<strong>on</strong> temperature between 35 and 45°C and its melting point is<br />

reported to be in <str<strong>on</strong>g>the</str<strong>on</strong>g> range <str<strong>on</strong>g>of</str<strong>on</strong>g> 225-230°C. PGA also exhibits a higher degree <str<strong>on</strong>g>of</str<strong>on</strong>g> crystallinity than PLA (~ 45-<br />

55 %), thus resulting in better mechanical properties but insolubility in water [Middlet<strong>on</strong> and Tipt<strong>on</strong>, 1998].<br />

<strong>The</strong> solubility <str<strong>on</strong>g>of</str<strong>on</strong>g> this polyester is somewhat unique, in that its high molecular weight form is insoluble in<br />

almost all comm<strong>on</strong> organic solvents (acet<strong>on</strong>e, dichloromethane, chlor<str<strong>on</strong>g>of</str<strong>on</strong>g>orm, ethyl acetate, tetrahydr<str<strong>on</strong>g>of</str<strong>on</strong>g>uran).<br />

<strong>The</strong> excepti<strong>on</strong>s are highly fluorinated organics such as HFIP (hexafluoroisopropanol) while low molecular<br />

weight oligomers sufficiently differ in <str<strong>on</strong>g>the</str<strong>on</strong>g>ir physical properties to be more soluble. Sutures <str<strong>on</strong>g>of</str<strong>on</strong>g> PGA lose<br />

about 50% <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g>ir strength after 2 weeks and 100% at 4 weeks, and are completely absorbed in 4~6 m<strong>on</strong>ths.<br />

Glycolide has been copolymerized with o<str<strong>on</strong>g>the</str<strong>on</strong>g>r m<strong>on</strong>omers to reduce <str<strong>on</strong>g>the</str<strong>on</strong>g> stiffness <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> resulting fibres<br />

[Middlet<strong>on</strong> and Tipt<strong>on</strong>, 1998].<br />

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