左旋型聚乳酸星狀巨單體與丙烯酸接枝共聚物之合成與性質鑑定

Synthesis and Characterization of Graft Copolymers from Star-shaped Poly(L-lactide) Macromonomers and Acrylic Acid

楊永怡(Young-I Yang)

指導教授 ： 王賢達

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2006年)

摘要

在此研究中，以陽離子開環聚合方式，將異戊四醇 (pentaerythritol)為起始劑，辛酸亞錫催化劑與左旋型聚乳酸(L-lactide)單體合成左旋型聚乳酸星狀巨單體(star-shaped macromonomer)。其尾端之-OH官能基與丙烯醯氯反應後形成雙鍵，產物純化後再與不同比例之丙烯酸以AIBN為起始劑，在氮氣下，溫度60˚C做游離基聚合，以形成接枝共聚物。
1H NMR光譜法可以決定左旋型聚乳酸星狀巨單體，改質星狀巨單體與接枝共聚物之分子結構。13C NMR可顯示左旋型聚乳酸星狀巨單體與接枝共聚物之共振信號。紅外線光譜(FTIR)與拉曼光譜(Raman)鑑定，其光譜顯示星狀巨單體，改質星狀巨單體與接枝共聚物之C=O和C=C官能基以及結晶振動信號。
凝膠滲透層析法(GPC)，其相對分子量數據顯示出在較少起始劑或是較多丙烯酸存在下，有較大的分子量。DSC熱分析數據顯示星狀巨單體和接枝共聚物皆有結晶存在。

關鍵字

聚乳酸 ； 聚丙烯酸 ； 接枝共聚物 ； 星狀物

並列摘要

In this study, star-shaped macromonomers of L-lactide were synthesized via cationic ring-opening polymerization with pentaerythritol (PENTA) and stannous octoate using as initiator and catalyst. The hydroxyl end groups of star-shaped poly(L-lactide) macromonomers were functionalized with acryloyl chloride in the presence of triethylamine. These modified macromonomers along with different molar ratios of acrylic acid monomers were initiated by 2,2-azobis(2-methyl propionitrile) (AIBN) at 60℃ under a N2 atmosphere to produce graft copolymers.
These polymers were characterized using 1H NMR, 13C NMR, FTIR, and Raman spectroscopies. 1H NMR and 13C NMR spectra showed characteristic signals PENTA (or end-groups), C=C double bonds, and acrylic unit, which came from star-shaped poly(L-lactide)s, modified macromonomers and graft copolymers. FTIR and Raman spectra also showed vibrational resonances of functional groups of these polymers. Besides, resonance signals for poly(L-lactide) crystalline of macromonomers and graft copolymers were identified.
Molecular weight data obtained from gel permeation chromatograms indicated trend of increasing upon decreasing PENTA or increasing acrylic acid concentrations in synthesis. Thermograms of differential scanning calormetry exhibited melting point of star-shaped macromonomers and graft copolymers.

並列關鍵字

Poly(L-lactide) ； Poly(acrylic acid) ； graft copolymer ； star-shaped

參考文獻

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