カテナン - 日本大学理工学部

平成 23 年度　日本大学理工学部　学術講演会論文集
N-8
Evaluation of Catenane Linkage in Main Chain of Vinyl Polymers by DSC
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2
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3
,
3
,
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*Satoru Ichikawa1, Daisuke Sasaki2, Toru Hoshi3, Toshiki Hagiwara3, Takashi Sawaguchi3
Abstract: Catenane is compound that cyclic molecules are mechanically interlocked. [2]catenane consists of two cyclic molecules.
The polymer including catenanes is expected as novel functional molecule by utilizing versatility of catenanes. However, there is
hardly the report on physical properties of catenanes. In this study, we synthesized [2]catenane triblock copolymer by ATRP of vinyl
momomers such as MMA, EMA and BMA using [2]catenane macroinitiator. Moreover, we evaluated catenane linkage in the main
chain of vinyl polymers by differential scanning calorimetry (DSC).
[2]
[2]
[2]
[1-3]
(ATRP)
[2]
(ATRP)
[2]
(Tg)
(DSC)
(Tg)
[2]
[4]
(PEMA Tg=65℃[4])
(PMMA Tg=120℃ )
(PBMA Tg=20℃[4])
5-
54-
U
BnO[2]
2Br[2]
ATRP
[2]
-
Br[2]
(Ⅰ)(CuBr) 2,2’-
(
:MMA
[2]
(2,2’-bpy)
:EMA
DMF
:BMA)
100℃
O
O
N
OH
O
O
Br
ATRP
NH
N
H
NH
H
N
HN
O
ATRP
O
O
O
O
Br
HN
n
O
NH
N
H
NH
H
N
O
HN
O
O
O
OR
Br
OH
N
N
OH
O
O
OH
N
O
HN
O
O
n
Br
O
OR
O
O
MMA:R=CH3, EMA:R=C2H5, BMA:R=C4H9
Scheme 1 Synthesis of [2]Catenane-Vinyl Polymer Triblock Copolymer.
( )
Graduate School of Science and Technology, Nihon Univ.
College of Science and Technology, Nihon Univ.
1189
San-ei Kogyo Corp.
平成 23 年度　日本大学理工学部　学術講演会論文集
[2]
Table ATRP of Vinyl Monomer Using [2]Catenane Macroinitiator.
ATRP
[I]/[M]
1
MMA
1/100
8700
1.46
3.9k-1k-3.9k
2
MMA
1/200
11000
1.34
5.0k-1k-5.0k
3
MMA
1/500
32000
1.66
15.5k-1k-15.5k
4
MMA
1/1000
81000
1.35
40.0k-1k-40.0k
[I]
5
EM A
1/100
6900
1.32
3.0k-1k-3.0k
1:1000
6
EM A
1/200
12000
1.43
5.5k-1k-5.5k
11.0k-1k-11.0k
ATRP
1:100
Run 1, 2
(2Cate-PMMA)
Tg
124℃
EM A
1/500
23000
1.36
EMA
BMA
8
BM A
1/100
11000
1.35
5.0k-1k-5.0k
9
BM A
1/200
21000
1.40
10.0k-1k-10.0k
10
BM A
1/500
42000
1.49
20.5k-1k-20.5k
a) Estimated by GPC (THF) based on Monodisperse PS Standard.
3
DSC
Run 1
Run 2
×10
3
3
120℃
Tg
Tg
4
6.6×10
2.1×10
Mw=2.7
80 110
130℃
2Cate-PMMA
Run 1 ; 2Cate-PMMA
Tg=124℃
Run 2 ; 2Cate-PMMA
PMMA
PMMA
Tg
PMMA
Tg
Run 5(2Cate-PEMA) Run 8(2Cate-PBMA)
DSC
2Cate-PEMA
Tg
Tg
37℃
∞)
65℃ PBMA
86℃
Tg=120℃
Run8
2Cate-PBMA
Tg
(Tg
0
20℃
20
40
60
80
100
120
140
Temperature (℃)
Fig.1 DSC Curves of 2Cate-PMMA.
[4]
20℃
Tg
Endo )
Tg
Tg=120℃
Run 3 ; 2Cate-PMMA
Run 5
PEMA
Tg∞
Heat Flow (
PMMA
Fig.2
compos ition ratio
7
PMMA
3
M w /M n
8.1×103
ATRP
Fig.1
M w ,G P C
(Mw)
Endo )
[M]
a)
monomer
GPC
MMA
a)
Run
Table
Run 5 ; 2Cate-PEMA
Tg=86℃
[1]M.Yamazaki, et.al., Synthetic Communi. 38, (4), 553-558,
(2008)
[2]M.Yamazaki, et. al., Koubunshi Ronbunshu, 65, (7),
Heat Flow (
Run 8 ; 2Cate-PBMA
Tg=37℃
496-498, (2008)
[3]T.Hagiwara, et. al., J. Res. Inst. Sci. Tech., Nihon Univ.,
124, 13-21, ( 2011)
0
20
40
60
80
100
120
140
[4]R.Pan, et. al., POLYMER HANDBOOK THIRD
Temperature (℃)
EDITION J.Brandrup and E.H.Innergut Ed., John Wiley &
Fig.2 DSC Curves of 2Cate-PEMA and 2Cate-PBMA.
Sons Inc. VI/394-396, (1989)
1190
a)

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