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聚胺酯形狀記憶材料之研究
學生 : 陳靖良 王泰元 葉志宏
指導教授 : 林鴻儒 博士
Department of Chemical and Materials Engineering, Southern Taiwan University
Introduction
1951 形狀記憶效應最早被美國依利諾大學發現
1959 日本Nakagawa定義形狀記憶行為：
材料易受先前之機械行為而產生易變回復之效果。
1965 美國海軍測量實驗室發現Ni-Ti合金具有形狀記憶行為
形狀記憶合金商品化產品：眼鏡框架、胸罩之鋼圈
Original shape
Deformation
Recovered shape
Introduction
1990 日本三菱重工發現聚胺酯亦具有形狀記憶行為
具生物相容性及生物降解性佳之PLGA為基底
製備具形狀記憶行為之聚胺酯
Application of PLGA
◆ Medical device
◆ Tissue engineering
◆ Release drug-deliver systems
◆ Tissue implants
以上圖片取自:http://www.city.yokkaichi.mie.jp/hospital/shinryoka/cardo-surg03.html
http://www.page.sannet.ne.jp/e-shirota/tuupefurontohifu.html
http://www.flickr.com/photos/kaurjmeb/150276483/
http://www.bonetumor.cc/html/19/57.html
Shape memory behavior
The shape was memorized
heating
Soften the
soft
segment
Stress
Cooling
The shape will be recovered from
the deformed shape to original shape
by changing temperature.
5
Fixed the shape
Research motivation
本研究使用聚乳酸與聚甘醇酸之共聚合物製備
PU。PLGA是一種不定形(amorphous)材料，在
生物體中可經由水解形成lactic acid和glycolic
acid，再經由代謝形成二氧化碳及水分子排出體
外，並且具有生物降解性及生物相容性的特性。
Research motivation
於是本研究即利用其生物降解及生物相容的特
性再加上形體記憶行為來合成出一系列PLGAbased polyurethane形狀記憶材料，並利用軟、
硬鏈節段組成的變化，探討分子形態與形狀記
憶效應的關係。
Material
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
PLGA (MW.5000) Polyol
Chloroform
Solvent
Diisocyanate
Hexamethylene diisocyanate (HDI)
4,4 Diphenylmethane di-isocyanate (MDI)
1,4-butanediol (BDO)
Chain extender
Experiment
N2
N2
50℃
Diisocyanate
PLGA-based polyurethane
50℃
Chain
extender
N2
60℃
Molding
Product of shape memory PU
模具
產品
實驗架構
形狀記憶聚胺酯
脂肪族異氫酸酯
聚醇類
鏈延長劑
聚胺類
鏈延長劑
芳香族異氫酸酯
聚醇類
鏈延長劑
聚胺類
鏈延長劑
FTIR、DSC 、機械性質、形狀記憶行為
脂肪族與芳香族系列
對形狀記憶行為之影響
Reaction Scheme
FTIR
Pre-polymer of PHB6
C=O
-NCO
PHB6
-NH
Transmittance
C=O
Pre-polymer of PMB6
C=O C=C
-NCO
PMB6
-NH
C=O C=C
4000
3500
3000
2500
2000
-1
Wavenumber (cm )
1500
1000
DSC
Sample
Glass transition
Tg (℃)
Tm (℃) of Soft
segment
Tm (℃) of Hard
segment
PHB2
18.92 ± 0.72
21.70 ± 1.21
-a
PHB4
19.78 ± 0.12
25.53 ± 2.09
-a
PHB6
20.13 ± 0.19
34.70 ± 1.94
80.44 ± 1.64
PHB8
23.47 ± 1.04
37.12 ± 0.35
85.69 ± 3.15
PHB10
25.16 ± 0.56
40.89 ± 1.67
91.53 ± 2.47
PMB2
19.23 ± 0.54
24.87 ± 3.18
80.21 ± 0.46
PMB4
19.95 ± 0.15
30.19 ± 1.42
82.56 ± 1.39
PMB6
21.87 ± 1.17
35.70 ± 2.12
90.87 ± 4.28
PMB8
30.40 ± 3.06
41.95 ± 3.57
96.15 ± 0.97
PMB10
35.42 ± 1.06
49.88 ± 1.83
107.48 ± 3.63
aThe
data was unavailable due to the structure of hard segment was not completed.
Mechanical properties
Shape memory behavior
the angle of recovery
recoverable ratio R (%) =
the original angle of bending
×100
Shape memory behavior
100
100
90
70
80
60
50
40
30
60
50
40
30
20
20
10
10
0
0
10
20
30
PMB2
PMB4
PMB6
PMB8
P M B 10
70
Ratio of recovery (%)
80
Ratio of recovery (%)
90
PHB4
PHB6
PHB8
P H B 10
40
50
o
Temperature ( C)
60
70
80
10
20
30
40
50
o
Temperature ( C)
60
70
80
Shape memory behavior
Sample
The recovered temperature Recovered timea (s)
at final recoverable
ratio (℃)
Final recoverable
ratio (%)
PHB2
-b
-b
-b
PHB4
36
30
27.0
PHB6
39
40
62.4
PHB8
55
70
85.0
PHB10
65
90
94.4
PMB2
30
20
16.0
PMB4
31
40
19.0
PMB6
40
50
23.0
PMB8
56
70
28.0
PMB10
62
100
30.0
aThe
time at which the final recovered ratio was reached by directly exposing the specimen to the recovered temperature.
could not be formed due to its low hard-segment content.
bPLGA2H
Shape memory behavior
100
100
90
90
80
80
70
70
60
o
30 C
o
40 C
o
50 C
o
60 C
50
40
30
Ratio of recovery (%)
Ratio of recovery (%)
91%
o
30 C
o
40 C
o
50 C
o
60 C
60
50
40
30
20
20
10
10
0
0
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
Time (sec)
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
Time (sec)
Conclusion

芳香族系列PU雖有優異的機械性質，
卻因執行形狀記憶行為時，受到分子
結構上苯環的立體障礙，導致差勁的
形變行為產生。

脂肪族系列PU具有較芳香族系列優異
之形變回復效果，並成功合成出於人
體體溫37℃時，其形狀恢復率約91%。
Thank you for your listening