1. 學生：謝明修 指導教授：王振乾

2. Abstract PLA 熔融混掺過程中，利用 hyperbranched polymer (HBP) 的氫氧官能基與 polyanhydride (PA) 行原位交聯反 應（ in-situ cross-linked ），形成 hyperbranched polymer- based 交聯粒子於 PLA 中。

3. Introduction 常見高分子的分子結構如 linear, branched, cross-linked, hyperbranched polymers (HBP) 都是新穎的添加物，樹狀類 的高分子由於具有獨特的結構和特性而受到矚目。 利用 hyper- branched polymer (HBP)-based 奈米結構的原位 （ in-situ ）合成，經由熔融技術製備出以 polylactide (PLA)-based 的奈米混掺。

4. Introduction (A) Chemical structure of the chief constituent of hyperbranched polymer (HBP). (B) Chemical structure of polyanhydride (PA). A. B.

5. Experimental Materials. Poly(lactic acid), PLA (Biomer L9000) (mol. wt.: 188 kDa from GPC) was obtained from Biomer, Germany. The PLA was the L-form of poly(lactic acid). The hyperbranched polymer (HBP), a dendritic polymer having the trade name BOLTORN H2004, mol. wt. 3200 g/mol was procured from Perstorp (Perstorp, Sweden). BOLTORN H2004 has six primary hydroxyl groups, with a hydroxyl value of 110-135 mg KOH/g and maximum acid number of 7 mg KOH/g. Polyanhydride, trade name PA-18 (LV), having an average molecular weight ~22500 g/mol was obtained from Chevron- Phillips, The Woodlands, Texas, USA. The PA is a linear polyanhydride resin having a 1:1 mole ratio of 1-octadecene and maleic anhydride.

6. Experimental Processing Parameters of Neat PLA and Its Blends Behavior of PLA and Its Blends after Dissolving in Methylene Dichloride

7. Experimental Schematic illustrations of in-situ cross-linking of hyperbranched polymer (HBP) in the PLA melt with the help of a polyanhydride (PA).

8. Results and Discussion SEM photomicrographs of extracted cross-linked HBP particles from the PLA matrix.

9. Results and Discussion FTIR spectrum: A: Neat PLA; B: HBP/PA particles (extracted), C: HBP/PA particles (outside); D: Hyperbranched polymer (HBP); E:polyanhydride (PA).

10. Results and Discussion Temperature dependence of the loss modulus (E”) of (A) neat PLA, (B) PLA/HBP (92/08) blend, and (C) PLA/HBP/PA (92/5.4/2.6) blend.

11. Results and Discussion Behavior of storage modulus,G’, of neat PLA and its blend as a function of oscillatory frequency (ω).

12. Results and Discussion Transmission electron micrographs of PLA having 8 wt.% of pristine HBP. (Scale bar: 50 nm).

13. Results and Discussion Transmission electron micrographs of PLA having crosslinked HBP. A: Scale bar: 200 nm; B: Scale bar: 100 nm.

14. Results and Discussion Tapping mode AFM phase image of the PLA/HBP/PA (92/5.4/2.6) blend revealed nanoscale domains of cross-linked HBP particles in the continuous PLA matrix. A: Scan size: 10 μm; B: Scan size: 5 μm.

15. Results and Discussion Stress-strain curves obtained at a cross-head speed of 15.4 mm/min: (A) neat PLA; (B) PLA/HBP (92/08); (C) PLA/HBP/PA (92/5.4/2.6). Tensile specimen after testing to failure at 15.4 mm/min under uniaxial tension.

16. Results and Discussion Mechanical Properties of Neat PLA and Its Blends

17. Results and Discussion Scanning electron micrographs of tensile fracture surfaces: A: Neat PLA; B: PLA/HBP (92/08); C: PLA/HBP/PA(92/5.4/2.6).

18. Conclusions HBP-based nanostructures 於 PLA matrix 相較於 unmodified PLA 可改善其 toughness 和 elongation at break 分別為 ~ 570% and ~847% 。 modified PLA 保有 high strength 和 modulus values 。 FTIR 和 DMTA 分析顯示 HBP 的交聯存在。 由 TEM 和 AFM 證實已交聯的 HBP 粒子於 PLA matrix 為 奈米級尺寸。