Download shaped and -shaped copolymers Star polymers 星形杂臂聚合物

高分子的设计与合成
洪春雁
潘才元
聚合物的结构 Architectures of polymers
线形聚合物 Linear polymers
均聚物
PE, PP, PS, PVC etc.
嵌段共聚物
A
B
无规共聚物
AS
交替共聚物
S
Linear polymers
ABA
(AB)n
ABC
ABCD
非线形聚合物
Nonlinear polymers
Grafting Polymer
Comb Polymer
接枝聚合物
梳形聚合物
H- shaped and -shaped copolymers
Combination of
two A blocks
A
B
A2B
A
B
A
B
-shaped copolymers
A
Combination
of two B blocks A
B
A
A
H-shaped copolymers
星形聚合物
Star polymers
星形杂臂聚合物 Miktoarm star polymers
 Mono-Dispersed
 Nano-Sized
 Egg-Like
 High density
of surface
Functional
groups
Hyperbranched
polymers
Umbrella Copolymer
伞形聚合物
Dumbbell-shaped copolymers
超支化聚合物
哑铃形聚合物
环状聚合物
Cyclic Polymers
H2C
CH2
P4VP
PS
H2C
CH2
原子转移自由基聚合
Atom Transfer Radical Polymerization, ATRP
ATRP or Atom Transfer Radical Polymerization is a
Polymerization reaction involving free radicals. It was
introduced as an extension to ATRA or Atom Transfer
Radical Addition by Jinshan Wang and Matyjaszewski,
(1995) and Sawamoto (1994/5).
Dr Krzysztof Matyjaszewski
J.C. Warner Professor of
Carnegie Mellon University
Department of Chemistry
4400 Fifth Avenue
Pittsburgh, PA 15213
Dr. Mistuo Sawamoto
Department of Polymer Chemistry
Graduate School of Engineering
Kyoto University, Kyoto
hv
Mask
PAG
PAG
O
O
O
O
O
PAG
PAG
O
O
O
O
O
n
PAG
H
O
O
n
O
O
PAG
N
n
O
O
n
O
O
O
n
n
3
n
PAG
N
O
O
SA
O
O
O
O
n
O
N
O
O
O
O
n
O
PAG
O
O
O
O
2
O
N
Biotinylated
Hydroxylamine
O
O
O
1
PAG
O
O
O
n
O
O
O
O
n
H
O
O
O
n
PAG
O
O
O
PAG
n
O
O
O
O
O
O
n
n
n
4
Mask
Streptavidin
Scale bar = 25 µm
RAFT Polymerization
RAFT= Reversible Addition-Fragmentation
Chain Transfer Polymerization
Dr. Graeme Moad
CSIRO Molecular and Health
Technologies,
Bayview Avenue, Clayton, Victoria
3168,
Australia
He joined CSIRO as a research scientist in 1979 and is currently a
chief research scientist. Dr Moad is coauthor of the book ‘The
Chemistry of Free Radical Polymerization’ which appeared as a
second edition in 2006. His research interests lie in the fields of
polymer design and synthesis (free radical polymerization, reactive
extrusion), polymerization kinetics and mechanism, and most recently
polymer nanocomposites.
Dr. Ezio Rizzardo
CSIRO Molecular and Health
Technologies,
Bayview Avenue, Clayton, Victoria
3168,
Australia
Ezio Rizzardo is a graduate of the University of New South Wales and
received his Ph.D. from the University of Sydney for his studies on the
photochemistry of nitro compounds. He joined CSIRO in 1976 after a
postdoc at Rice University, RIMAC, and the Australian National
University. His CSIRO research has focused on developing methods for
controlling free radical polymerization. For this he has received a
number of awards including the RACI Australian Polymer Medal and the
CSIRO Chairman’s Gold Medal. Currently he is a CSIRO Fellow and a
Fellow of the Australian Academy of Science.
Dr.San H. Thang
CSIRO Molecular and Health
Technologies,
Bayview Avenue, Clayton, Victoria 3168,
Australia
San H. Thang was born in Saigon, Vietnam, in 1954 and came to Australia
in 1979 as a refugee. He completed his B.Sc.(Hons) degree in 1983 and
Ph.D. in 1987 from Griffith University. He joined CSIRO in 1986 as a
research fellow. He then moved to ICI Australia in late 1987 to undertake
the challenge of industrial research. He returned to CSIRO in late 1990,
and in 1995 he was co-inventor of the RAFT Process. He is currently a
senior principal research scientist at CSIRO Molecular and Health
Technologies where his research focuses on the interface between organic
and polymer chemistry.
Click Chemistry
蝌蚪形聚合物的合成
R S
O
O
S
RAFT
S
St
S
O
RAFT
S
O
S
O
O
N3-C2H4-OH
S
S
O
O
O
O OH
S
S
O
N3C2H4O
NIPAM
"click"
reaction
N3
CH2 C C
N
N
PNIPAAM;
PSt
N
CH2
Thiol-Click
Michael addition reaction
(a) Arthur Michael (1855–1942), who discovered the Michael
addition reaction. (b) Schematic depiction of the Michael
addition reaction.
General carbon-Michael reaction mechanistic scheme.
Second Michael addition of acetoacetate group to methyl acrylate.
Michael Addition involving an alkyne acceptor.
Higher reactivity of secondary amines in aza-Michael addition reactions.
Dendrimer
Amino Acid
Alanine
Arginine
Asparagine
Aspartic acid
Cysteine
Glutamic acid
Glutamine
Glycine
Histidine
Isoleucine
Leucine
Lysine
Methionine
Phenylalanin
Proline
e
Serine
Threonine
Tryptophan
Tyrosine
Valine
Side chain polarity
Ala
Arg
Asn
Asp
Cys
Glu
Gln
Gly
His
Ile
Leu
Lys
Met
Ph
Pro
e
Ser
Thr
Trp
Tyr
Val
A
R
N
D
C
E
Q
G
H
I
L
K
M
F
P
S
T
W
Y
V
nonpolar
polar
polar
polar
nonpolar
polar
polar
nonpolar
polar
nonpolar
nonpolar
polar
nonpolar
nonpolar
nonpolar
polar
polar
nonpolar
polar
nonpolar
Hydropathy index
neutral
positive
neutral
negativ
neutral
e
negativ
neutral
e
neutral
positive
neutral
neutral
positive
neutral
neutral
neutral
neutral
neutral
neutral
neutral
neutral
1.8
-4.5
-3.5
-3.5
2.5
-3.5
-3.5
-0.4
-3.2
4.5
3.8
-3.9
1.9
2.8
-1.6
-0.8
-0.7
-0.9
-1.3
4.2
Synthesis of L-valine and L-leucine type Ib dendrimers: (a) Boc-Gly-OH,
DCC, DMAP-DCM; (b) TFA-DCM; (c) active ester, HOBt, DIEA, DMFDCM; (d) Ac2O, DIEA-DC
Is Dendrimer an Antenna?
Photon
Cis- and trans- transformation of
azobenzene
Irradiation at 1600 cm-1 can make the transformation
of cis- to trans-?
Photoisomerization of Azodendrimer
by Harvesting of Low Energy Photons
Photons (1600 cm-1)
G2 dendrimers containing Coumarin-2 as an energy donor and
Coumarin-343 as an energy acceptor (left) and dendrimers without
Coumarin-343 chromophore (right) for relative rate study.
Organic Light Emitting Diodes
Catalysis
http://perceco2.chem.upenn.edu/~percec/inthenews/denx.html
http://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART
Nanowires
Dendrimers Fighting the Spread of Diseases
The dendrimers (blue and red) in VivaGel interact with
The dendrimer (blue and red) attaches to multiple receptors
protein structures (yellow) on the surface of HIV, blocking
(pink) on cell membranes or other biological structures such
the interaction of HIV (purple) with healthy human cells
as a virus.
(pink) that results in HIV infection.
Illustrations courtesy of Starpharma Pooled Development, Ltd
基于树枝状大分子的智能型纳米容器设计合成
O
O
O
O
O
O
O
CO O
OH
CO
CO O
COOH
O
O
O
OH
C
H
OO
O
CO
OH
O
COO
CO
O
O
CO
OH
O
O
CO
OH
O
O
CO
O
O
O
O
O
O
OH
O
O
O
COOH
O
O
O
O
OH
HO
O
CO
O
O
HO
COOH
COOH
HO
HO
O
COO
O
O
O
O
O
COO
H
O
O
COO
CO
OH
O
O
OH
O
O
O
OH
S
C OO
O
O
CO
O
O
COOH
O
COO
HO
O
OH
O
CO
O
HO
CO
O
OH
O
O
O
CO
O
O
COO
OH
COO
O
O
OH
COOH
HO
CO
COOH
OH
O
O
O
CO
OH
HS
S
C OO
O
OH
COO
O
O
O
COOH
S
O
O
O
O
O
O
O
O
O
COO
O
S
OH
S
O
S
NIPAM
RAFT
O O O
O
O O
O
O
O
O
S
O
CO
S
S
S
S
S
S
S
COO
O
CO
H
CO
OH
O
CO
CO
S
O
O
S
O
COOH
O
CO
O
COO
CO
O
O
CO
O
S
OH
O
COOH
S
S
CO
S
O
CO
OH
O
OH
O
CO
O
COO
COOH
O
S
CO
O
COOH
S
S
O
S
O
O
O
O
S
CO
CO
O
CO O
COOH
O
O
S
S
O
O
COO
S
COOH
CO
OH
O
CO
S
S
H
S
S
O
CO
S
O
O
O
O
O
O O O
O
O O
O
O
O
O O O
O
O O
O
O
O
O
O
T
O
O
O
O
O
O O O
O
O O
O
T
O
O
O
O
O
O
O
O
O
O
O
O
O
25 oC
O
O
O
O
O
O
O
O
O
O
O
O
40 oC
O
O
O
O
O
用化学修饰可以改善溶解、分散、加工性能，但是破坏了碳纳米管的结构。
如何在改善溶解、分散、加工性能的同时，保持碳管的自身性能不被破坏？
可先对碳管进行轻微修饰，把Dendrimer接到碳管的表面，尽管接枝密度很
低，碳管的溶解、分散、加工性能也得到了很大提高。
Hyperbranched Polymer
Couple-monomer methodology (CMM)
O
O
CH2=CHCNHCH2CH2SSCH2CH2NHCCH=CH2
+
HN
NH2
N
NH2
H2N
NH
N
H2N
N
N
H2N
NH2
NH2
N
N
N
N
N
H2N
NH2
N
N
H2N
H2N
N
NH2
H2N
NH2
N
NH2
WU
(330~3
85nm)
Normalized Photoluminescence
Intensity
Normalized Photoluminescence Intensity
No
filter
b
WB
(460~4
90nm)
450
WG
(510~5
50nm)
550
500
600
650
Wavelength (nm)
400
500
600
Wavelength (nm)
700
800
－The End－
Thank You！