生物分解性凝膠之製備與性質研究

STUDIES ON PREPARATION AND PROPERTIES OF THE BIODEGRADABLE HYDROGELS

汪佳儀(Jia-Yi Wang)

指導教授 ： 李文福

大同大學/工程學院/化學工程學系所/碩士(2008年)

摘要

本文包含三個研究主題，第一部分研究是合成一系列溫感且生物可分解性Poly(N-isopropyl acrylamide) Poly(NIPAAm)水膠，其係由NIPAAm 與PLGA-PEG-PLGA
diacrylate(PELGAdA)為交聯劑製備而成的，PELGAdA係由Poly(ethylene glycol) 為起始劑，辛酸亞錫[Sn(Oct)2]為觸媒將Lactide 及Glycolide 開環聚合後所得PLGA-PEG-PLGA diol，再用丙烯醯氯乙烯化後所得者。其研究主要探討PELGAdA 不同LA/GA 比，及不同交聯劑對膠體膨潤行為與機械強度的影響。結果顯示，交聯劑添加量的減少和GA 在交聯
劑含量的增加，膨潤動力也跟著增加。而膠體的交聯密度、機械強度隨著交聯劑含量以及LA 在交聯劑中含量增加而增加。而疏水的PLGA 鏈段的交聯劑的膠體轉移溫度比用NMBA 為交聯劑為低。以NMBA 為交聯劑的膠體強度、交聯密度也較低。此系列膠體展現良好的溫度及生物降分解性。
本論文的第二部分是合成一系列溫感且生物可分解性2-(hydroxyethyl methacrylate) (HEMA) 水膠， 是以具生物相容性2-(hydroxyethyl methacrylate) (HEMA)與親水性的PEG diacid 和疏水性的PCL diol 聚縮合而成之PCL-PEG600-PCL diol，再以丙烯醯氯低溫乙烯化合成為PCL-PEG600-PCL diacrylate (PCE6dA)ABA 三團聯親兩性共聚交聯劑製
備而成的系列膠體。在膠體中交聯劑的含量影響膨潤動力、其膠體機械性質、熱性質以及生物降解的型態變化。結果顯示，交聯劑的添加降低膨潤動力; 機械性質方面加入交聯劑PCE6dA 比加入交聯劑EGDMA 強度強。加入PCE6dA 為交聯劑增加了生物分解性。
本論文的最後一部分是合成一系列溫感且生物可分解性2-(hydroxyethyl methacrylate) (HEMA) 水膠， 是以具生物相容性2-(hydroxyethyl methacrylate) (HEMA)與親水性的PEG diacid 和疏水性的PCL diol 聚縮合而成之PCL-PEG2000-PCL diol，再以丙烯醯氯低溫乙烯化合成為PCL-PEG2000-PCL diacrylate (PCE20dA)ABA 三團聯親兩性共聚交聯劑製
備而成的系列膠體。在膠體中交聯劑的含量影響膨潤動力、其膠體機械性質、熱性質以及生物降解的型態變化。結果顯示，交聯劑的添加降低膨潤動力; 機械性質方面加入交聯劑PCE20dA 比加入交聯劑EGDMA強度強。加入PCE20dA 為交聯劑增加了生物分解性。

關鍵字

聚[乙二醇/己內酯]二丙烯酯 ； 聚丙交酯乙交酯 ； 異丙基丙烯醯酸 ； 生物分解性 ； 甲基丙烯酸羥乙酯

並列摘要

This thesis consists of three parts.The first part deals with A series of temperature sensitive and biodegrabable hydrogels porous
hydrogels, this series gels were preparedby copolymerizing.
N-isopropylacrylamide (NIPAAm), and the PLGA-PEG-PLGA its triblock
diacrylate polymers which as the crosslinker were synthesized by ring open
polymerization (ROP) of lactide and glycolide using poly(ethylene glycol)
and stannous octoate [Sn(Oct)2] as catalyst followed by the functionality of
acrylated group with acryloyl chloride at low temperature. The effect of
different LA/GA ratios of the NIPAAm/PELGAdA copolymeric hydrogel
on the swelling ratio and mechanical properties for the poly(NIPAAm)
hydrogels were investigated. The results showed that the swelling ratio of
the gel in deionized water increased with an increase of the content of
crosslinker segment in the NLG hydrogels and the swelling ratio increased
with an increase of the GA content in the copolymeric hydrogel. The
mechanical strength, crosslinking density, compressive modulus decrease
with an increase of crosslinker and the more LA ratio in the copolymeric
hydrogel. The results showed that the critical gel transition temperatures
(CGTT) of the gels crosslinked with PELGAdA were lower than those of the
gels crosslinked with NMBA due to the hydrophobicity of the PLGA
segment. The results also showed that the gels crosslinked with PLGAdA
had higher mechanical strength and crosslinking density than gels
crosslinked with NMBA. The gels showed good temperature sensitive and
biodegradable behavior.

The second part of this thesis describes A series of biodegradable porous hydrogels, based on biocompatible
2-hydroxyethyl methacrylate (HEMA) and a crosslinker of ABA type
amphiphilic triblock copolymers were synthesized by the condensation of
hydrophobic polycaprolactone diol (PCL diol) with hydrophilic dicarboxy
poly(ethylene glycol diacid) (PEG diacid) obtained by reacting
poly(ethylene glycol) (PEG) (Mw=600) with succinic anhydride. The
PCL-PEG600-PCL diol triblock copolymers were then acrylated with
acryloyl chloride to produce PCL-PEG600-PCL diacrylates (PCE6dA) at low
temperature. The effect of the crosslinker content on the swelling behaviors
and physical properties for the poly(HEMA) hydrogels were, thermal
behavior, swelling ratio, and morphological characteristics as well as
biodegradability of the presented gels were investigated. The results showed
that the swelling ratio of the gel in deionized water decreased with an
increase of the content of crosslinker (PCE6dA) segment in the poly(HEMA)
hydrogels. And the effect that properties of the gels crosslinked with
hydrophobic PCE6dA added. The results also showed that the gels
crosslinked with PCE6dA had higher mechanical strength and crosslinking
density than the gels crosslinked with EGDMA. The gel were crosslinked
with PCE6dA enhance the biodegradable.

The final part of thesis reports A series of biodegradable porous hydrogels, based on biocompatible
2-hydroxyethyl methacrylate (HEMA) and a crosslinker of ABA type
amphiphilic triblock copolymers were synthesized by the condensation of
hydrophobic polycaprolactone diol (PCL diol) with hydrophilic dicarboxy
poly(ethylene oxide) (PEG diacid) obtained by reacting poly(ethylene glycol
diacid) (PEG diacid) (Mw=2000) with succinic anhydride. The
PCL-PEG2000-PCL diol triblock copolymers were then acrylated with
acryloyl chloride to produce PCL-PEG2000-PCL diacrylates (PCE20dA) at
low temperature. The effect of the crosslinker content on the swelling
behaviors and physical properties, thermal behavior, and morphological
characteristics as well as biodegradability of the presented gels were
investigated. The results showed that the swelling ratio of the gel in
deionized water decreased with an increase of the content of crosslinker
(PCE20dA) segment in the poly(HEMA) hydrogels. And the effect that
properties of the gels crosslinked with hydrophobic PCE20dA added. The
results also showed that the gels crosslinked with PCE20dA had higher
mechanical strength and crosslinking density than the gels crosslinked with
EGDMA. The gel were crosslinked with enhance the biodegradable.

並列關鍵字

polycaprolactone diacrylate ； LCST ； PLGA ； N-isopropylacrylamide ； 2-hydroxyethyl methacrylate ； biodegradable

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