Modern Polymerization Techniques

Materials Science
TM
Volume 5, Number 1 2010
Start living with controlled polymerization
Reversible Addition Fragmentation
Chain Transfer (RAFT) Polymerization
Block Copolymer Synthesis Using a
Commercially Available Nitroxide-
Mediated Radical Polymerization
(NMP) Initiator
ATRP for Everyone: Ligands and
Initiators for the Clean Synthesis of
Functional Polymers
Asymmetric Polymerization in a
Chiral Liquid Crystal Reaction Field
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Material Matters (ISSN 19339631) is a publication of Aldrich
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Group. 2010 Sigma-Aldrich Co.
TM
Vol. 5, No. 1 2010
About Our Cover
Methods of living radical polymerization can be used to synthesize polymers with well-defined
molecular weight and functional end-groups designed to self-assemble and form nanostructures
or to selectively modify surfaces of inorganic solids. Our cover illustrates the living growth of
polymer chains characteristic of these technologies. An ATRP synthesis of a block copolymer
illustrated in the top part of the picture shows the copper initiating species (tiny spheres) close to
a hydroxy initiator at the beginning of the growing polymer chain. Below it synthesis of random
copolymer is controlled by an attached RAFT agent. The universal NMP initiator is also shown in
the blue sphere to the right.
Introduction
Welcome to the first 2010 issue of Material Matters focusing on
Modern Polymerization techniques for making polymers with well-defined
properties and molecular architectures. With this issue, we are pleased
to announce the increased emphasis of Sigma-Aldrich Corporation on
serving you, the customers of Aldrich Materials Science. Over the coming
year we will invest to expand our offer of products for materials research.
A significant portion of this investment will be in Polymer Science and
includes additional tools for polymer synthesis as well as greater selection
of novel polymer materials. The many new products for living radical and
electrochemical polymerization presented in this issue are the first result
of this investment. Another benefit from this investment is the center of
excellence for custom monomer and polymer synthesis announced on p. 8 of this issue. We are
committed to supplying you with the highest quality materials needed for your research, so that
you can focus on results!
Living and template-assisted polymerization methods developed over the last decade have
changed the way we think about polymer materials. We are no longer limited to making simple
polymers heterogeneous in terms of their molecular weight and conformation. It is now possible
to prepare polymers with precise nanometer scale architectures designed to confer useful
properties to the resulting polymer materials that find increased use in applications ranging from
advanced coatings to molecular electronics. Three revolutionary methods that give living character
to the well-known radical polymerization process are especially powerful: (i) Reversible Addition-
Fragmentation Chain Transfer (RAFT) polymerization, (ii) Nitroxide-Mediated Polymerization (NMP),
and (iii) Atom-Transfer Radical Polymerization (ATRP). Each of the three methods is useful and, in
practice, the choice between them often comes down to availability of the necessary reagents. You
will find the initiators, ligands, and chain transfer agents needed to carry out all three techniques
in product tables that accompany the articles in this issue. A selection of electropolymerizable
thiophene and pyrrole monomers useful in the context of template-assisted synthesis of polymer
materials is also featured in this issue.
The issue begins with an article by a team of CSIRO researchers who discovered and significantly
developed the RAFT process. They provide an overview of the RAFT polymerization technique and
explain criteria for choosing a RAFT agent appropriate for a given monomer. In the following article
Professor Karen Wooley and her student Nam Lee from Texas A&M University illustrate the NMP
process by describing synthesis of a well-defined diblock copolymer using NMP initiators available
from Aldrich Materials Science. Professor Krzysztof Matyjaszewski and his colleagues discuss the
recently developed improvements to ATRP and also provide practical recommendations regarding
the choice of the appropriate reagents. Finally, Professor Kazuo Akagi from Kyoto University reports
the recent synthesis of films containing helical polyacetylene which were templated by a chiral
liquid crystal.
Each article in this issue is accompanied by a list of monomers available from Aldrich Materials
Science. Please contact us at [email protected] if you need any monomer that is not available in
our catalog, or would like custom packaged quantities of monomers for your development work.
We welcome your product requests and suggestions as we continue to grow our Polymer Science
product offer.
Kaushik Patel, Ph.D.
Materials Science
Sigma-Aldrich Corporation
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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exo-5-Norbor nene carboxy lic acid
(1R,2S,4R)-Bicyclo[2.2.1]hept-5-ene-2-carboxy lic
acid [934-30-5] C
8
H
10
O
2
FW 138.16
718149-1G 1 g
718149-5G 5 g
References
(1) Fu, Q.; Seery, T. A. P. Polym. Prepr. 2001, 41 (1), 341-342.
(2) Pollino, J. M.; Stubbs, L. P.; Weck, M. Macromolecules 2003, 36, 2230-2234.
(3) Gordon, E. J.; Gestwicki, J. E.; Strong, L. E.; Kiessling, L. L. Chem. Biol. 2000, 7, 9-16.
(4) Strong, L. E.; Kiessling, L. L. J. Am. Chem. Soc. 1999, 121, 6193-6196.
(5) Owen, R. M.; Gestwicki, J. E.; Young, T.; Kiessling, L. L. Org. Lett. 2002, 4,
2293-2296.
Joe Porwoll, President
Aldrich Chemical Co., Inc.
Your Materials Matter.
Polymerization Tools Featured in this Issue
Materials Category Content Page
RAFT Agents A list of available RAFT materials for living radical polymerizations 5
Radical Initiators A selection of available radical initiators 5
Methacrylamide Monomers A selection of available methacrylamide monomers 6
Methacrylate Monomers A selection of available methacrylate monomers 6
NMP Initiators Initiators for Nitroxide Mediated Polymerization (NMP) 12
Vinyl Amide and Vinyl Ester Monomers A selection of available vinyl amide and vinyl ester monomers 12
Styrene Monomers A selection of available functionalized and substituted styrene monomers 13
Ligands for ATRP Ligands that efectively bind copper ions required to promote ATRP 20
ATRP Initiators Materials used to prepare polymers with end-chain functionalities by ATRP 21
Metal Catalysts for ATRP Cu(I) and Cu(II) salts for ATRP polymerization 21
Acrylate Monomers A selection of mono & polyfunctional acrylate monomers 22
Acrylamide Monomers A selection of acrylamide monomers 24
Thiophene and Pyrrole Monomers A selection of thiophene and pyrrole monomers 28
Do you have a compound that you wish Sigma-Aldrich could list to
help materials research? If it is needed to accelerate your research,
it mattersplease send your suggestion to [email protected] and we
will be happy to give it careful consideration.
Professor Karen Wooley of Texas A&M University kindly suggested
that we offer the exo-5-Norbornene-carboxylic acid (Aldrich Prod.
No. 718149) as a product in our catalog. This compound is a functional,
stereochemically pure monomer used in ring opening metathesis
polymerization (ROMP) synthesis of well-defined polymer materials.
The pure exo- monomer shows faster reaction times,
1
higher conversion
ratios, and better control of ROMP synthesis
2
compared to the racemic
analog. The carboxylic acid serves as a versatile handle that can be
used to prepare a variety of polymers (e.g., glycopolymers) for
biomedical applications.
3-5
COOH
Reversible Addition Fragmentation Chain Transfer
(RAFT) Polymerization
Graeme Moad*, Ezio Rizzardo, and San H. Thang
CSIRO Molecular and Health Technologies
Bayview Ave., Clayton, Victoria 3168, Australia
*Email: [email protected]
Introduction
RAFT (Reversible Addition Fragmentation chain Transfer) polymerization
is a reversible deactivation radical polymerization (RDRP) and one of the
more versatile methods for providing living characteristics to radical
polymerization.
1-7
The historical development of RAFT polymerization at
CSIRO has been outlined.
1
Advantages of RAFT polymerization include:
The ability to control polymerization of most monomers polymerizable
by radical polymerization. These include (meth)acrylates, (meth)
acrylamides, acrylonitrile, styrenes, dienes and vinyl monomers.
Tolerance of unprotected functionality in monomer and solvent
(e.g., OH, NR
2
, COOH, CONR
2
, SO
3
H). Polymerizations can be carried
out in aqueous or protic media.
Compatibility with reaction conditions (e.g., bulk, organic or aqueous
solution, emulsion, mini-emulsion, suspension).
Ease of implementation and inexpensive relative to competitive
technologies.
In an ideal living polymerization, all chains are initiated at the beginning
of the reaction, grow at a similar rate and survive the polymerization:
there is no irreversible chain transfer or termination. If initiation is rapid
with respect to propagation, the molecular weight distribution is very
narrow and chains can be extended by further adding monomers
into the reaction. In a radical polymerization all chains cannot be
simultaneously active. In RDRP, such as RAFT polymerization, these
attributes are displayed in the presence of reagents that are capable of
reversibly deactivating propagating radicals such that the majority of
living chains are maintained in a dormant form, and reaction conditions
that support a rapid equilibrium between the active and dormant
chains (Figure 1).
Dead chains
Propagating radicals
= active chains
'R' RAFT
ends
Initiator-
derived ends
ZC(=S)S RAFT ends
= dormant chains
Figure 1. RAFT Polymerization Schematic.
4
The number of chains of each type shown
here is not in proportion to that expected for a well-designed experiment. On average,
all living chains grow simultaneously and have equal chain length because equilibration
of the dormant and active chain ends is rapid with respect to propagation. A RAFT agent
is represented as ZC(=S)S.
Under these conditions, molecular weights can increase linearly with
conversion, molecular weight distributions can be very narrow
(Figure 2) and the majority of the polymerization product should
comprise of dormant chains.
10
6
dead chains
Living (dormant)
chains
10
5
10
4
10
3
Molecular Weight (g/mol)
Figure 2. Typical molecular weight distributions for a conventional and a RAFT
polymerization of styrene under similar experimental conditions.
4
The mechanism of chain activation/deactivation in RAFT is shown in
Scheme 1. The reactions associated with RAFT equilibria are in addition
to those (i.e., initiation, propagation and termination) that occur during
conventional radical polymerization. In an ideal RAFT process, the RAFT
agent should behave as a transfer agent. Termination is not suppressed
by the RAFT process. Retention of the thiocarbonylthio groups in the
polymeric product is responsible for the living character of RAFT
polymerization and renders the process suitable for synthesizing block
copolymers and end functional polymers. Removal or transformation of
the thiocarbonylthio group may be required for some applications. A
number of methods to accomplish the end group removal have been
devised and can be readily incorporated into polymer syntheses.
10, 12-16
R' + S S
Z
R
k
add
k
-add
S S
Z
R' R
k

S S
Z
R' R +
Reactive
double bond
Z modifes addition and
fragmentation rates
1
Weak single bond
2 3
R must be a good homolytic leaving
group and a good inititating species
Scheme 1. Mechanism for reversible addition-fragmentation chain transfer (RAFT)
Selection of the RAFT agent (ZC(=S)SR) for the monomers and reaction
conditions is crucial for the success of a RAFT polymerization
experiment. However, this should not be a daunting task. The
effectiveness of RAFT agents is determined by the substituents R and Z
and guidelines for selection have been proposed (Figure 3).
1, 3
Polymerization of most monomers can be well-controlled to provide
minimal retardation and a high fraction of living chains by using one of
just two RAFT agents. The first class is suited to more activated
monomers (MAM) such as methacrylics, e.g., methyl methacrylate (MMA,
Aldrich Prod. No. M55909), methacrylic acid (MAA, Aldrich Prod.
No. 155721), hydroxypropyl methacrylamide (HPMAM) and acrylics,
e.g., methyl acrylate (MA, Aldrich Prod. No. M27301), acrylic acid
(Aldrich Prod. No 147230), acrylamide (AM, Aldrich Prod. No. 148660),
acrylonitrile (AN, Aldrich Prod. No. 320137), styrene (St, Aldrich Prod.
No. W323306). The second class of RAFT agents is suited to less
activated monomers (LAM) such as vinyl acetate (VAc, Aldrich Prod.
No. V1503), N-vinylpyrrolidone (NVP) or N-vinylcarbazole (NVC).
2
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Recently, a switchable RAFT agent that can be used to control
polymerization of both MAMs and LAMs has been described.
8, 9
Requirements for specific end-functionality or polymer architecture
may dictate the use of other RAFT agents.
10, 11
Z: Ph >> SMe N > >
N
H
N
Me
~ Me >>
N
O
> OPh > OEt ~
N
N
Me
~
N
Me
> N(Et)2
VAc, NVP, NVC MMA, HPMAM
St, MA, AM, AN
R: CN
CH3
CH3
~ Ph
CH3
CH3
> Ph
H
CN
> COOEt
CH3
CH3
>> CH2
CH3
CH3
CH3
CH3
CH3 ~
CH3
H
CN ~
H
CH3
Ph ~
CH3
CH3
CH3 ~
H
H
CN ~
H
H
Ph
St, MA, AM, AN
VAc, NVP, NVC
MMA, HPMAM
Figure 3. Guidelines for selection of RAFT agents (Z-C(=S)S-R) for various
polymerizations.
1, 3
For Z, addition rates and transfer constants decrease and
fragmentation rates increase from left to right. For R, fragmentation rates decrease
from left to right. A dashed line indicates limited control (e.g., retardation, high
dispersity likely).
With appropriate choice of reagents and polymerization conditions
RAFT polymerization can be used in the synthesis of well-defined homo,
gradient, diblock, triblock and star polymers, as well as more complex
architectures including microgels and polymer brushes. Applications
now being reported range from novel surfactants, dispersants, coatings
and adhesives, to biomaterials, membranes, drug delivery media,
electroactive materials and other fields falling under the nano-
technology umbrella.
RAFT Polymerization of More-Activated
Monomers (MAMs)
Good control over polymerization of a MAM is observed with
trithiocarbonates (Z=S-alkyl, e.g., 4-6). Z is preferably based on a thiol
with low volatility. Aromatic dithioesters (Z=aryl, e.g., 9, 10) are amongst
the most active RAFT agents and show general utility in the
polymerization of MAMs.
1, 2
However, the aromatic substituted RAFT
agents may give retardation when used in high concentrations and are
more sensitive to hydrolysis and decomposition induced by Lewis
acids.
17, 18
Alkyl-substituted RAFT agents (4-6) can be tried if hydrolysis is
a concern. The bis(thiocarbonyl) disulfides 7 and 8 are useful as
precursors to the tertiary RAFT agents and can be used to form a RAFT
agent in situ during polymerization.
19
C12H25S
S
S
CN
4
Aldrich Prod. No. 723037
5
Aldrich Prod. No. 723274
C12H25S
S
S
CN
CO2H
C
12
H
25
S
S
S
CN
6
Aldrich Prod. No. 723029
7
Aldrich Prod. No. 723126
C
12
H
25
S
S
S S
SC
12
H
25
S
S
S S
S
8
Aldrich Prod. No. 723118
9
Aldrich Prod. No. 722987
S
S
CN
10
S
S
Ph
Figure 4. A series of RAFT agents that show good polymerization control for MAMs.
R must efficiently reinitiate polymerization and must be a good
homolytic leaving group with respect to the propagating radical.
20
R must also be efficient in reinitiating polymerization: it should add to
monomer rapidly with respect to the rate of propagation. A good
choice for the case of acrylates and acrylamides is the RAFT agent 6 with
R=cyanomethyl. The choice of R is critical in the case of methacrylates.
In some of the most effective RAFT agents R is tertiary cyanoalkyl
(e.g., 4, 5, 9). The utility of the RAFT process is illustrated by the following
example of RAFT polymerization of methyl methacrylate (MMA). A series
of high (80-100%) conversion MMA polymerizations were carried out at
90 C with 1,1-azobis(1-cyclohexanecarbonitrile) initiator, and using an
~60-fold range of concentrations of S-dodecyl S-(2-cyano-4-carboxy)but-
2-yl trithiocarbonate 5.
10
The molecular weight distributions observed
after six hours are shown in Figure 5. The molecular weights, ranging
from 2,600 to 125,000, agree with expectation based on the
concentrations of RAFT agent and initiator used.
10
All samples have
narrow molecular weight distributions (PDI <1.2).
10
6
Molecular Weight (g/mol)
10
5
10
4
10
3
10
2
[RAFT]=0.003 M, M
n
=125,000, =1.16
[RAFT]=0.012 M, M
n
=39,600, =1.09
[RAFT]=0.025 M, M
n
=20,600, =1.09
[RAFT]=0.10 M, M
n
=4,600, =1.15
[RAFT]=0.20 M, M
n
=2,600, =1.17
[RAFT]=0.05 M, M
n
=9,300, =1.11
[RAFT]=0.006 M, M
n
=84,000, =1.11
Figure 5. Molecular weight distributions for PMMA formed by high conversion RAFT
polymerization of MMA (6.55 M in benzene) with 1,1-azobis(1-cyclohexanecarbonitrile)
(0.0018 M) as initiator and various concentrations of RAFT agent 5 for 6 h at 90 C.
10
3
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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RAFT Polymerization of Less-Activated
Monomers (LAMs)
The less active RAFT agents with Z=NR
2
(dithiocarbamates), Z=OR
(xanthates) and R = alkyl or aryl offer good control. The more active
RAFT agents Z=R (dithioesters) or SR (trithiocarbonates) inhibit
polymerization of a LAM. The choice of R group is also critical because
most monomers in the class have a high propagation rate constant.
Inhibition periods due to slow reinitiation are expected for RAFT agents
such as 12 and 13. One preferred RAFT agent is 11. Examples of VAc
polymerization with 11 are shown in Table 1.
7
Table 1. RAFT Polymerization of Vinyl Acetate
7
Monomer
(M)
RAFT
Agent
(M10
2
)
Initiator
a
(M10
3
)/
Conditions
Conv
% Mn
b
M
n
(calc)
c
PDI
10.86 11 (4.98) AIBN (61)
60 C 16 h
96 22,700 18,000 1.24
7.24 11 (5.06) ACHN (28)
75 C 16 h
93 13,400 11,440 1.29
7.24 11 (10.06) ACHN (28)
75 C 16 h
95 7,100 5,880 1.25
a
AIBN: 2,2-azobis(isobutyronitrile) (Aldrich Prod. No. 441090);
ACHN: 1,1-azobis(cyclohexanecarbonitrile) (Aldrich Prod. No. 380210)
b
number average molecular weight in polystyrene equivalents.
c
calculated molecular weight based on complete consumption of RAFT agent.
N
S
S
CN
11
Aldrich Prod. No. 723002
O
S
S
CN
12
O
S
S
13
O
S
S
CN
14
Figure 6. A series of RAFT agents that show good polymerization control for MAMs.
Switchable RAFT Agents
We recently reported on a new class of stimuli-responsive RAFT agents
that can be switched to offer good control over polymerization of both
MAMs and LAMs and thus a more convenient route to polyMAM-block-
polyLAM polymers with narrowed molecular weight distributions.
9
This
approach was demonstrated with the use of 4-pyridinyl-N-methyldi-
thiocarbamate derivatives to prepare PMMA-block-PVAc and PMA-block-
PNVC. The N-4-pyridinyl-N-methyldithiocarbamates provide effective
control over polymerization of LAMs (Scheme 2) and when protonated
also provide excellent control over the polymerization of MAMs.
9
N
S
S
N
R
N
S
S
N
R
base H
+
N
S
S
N
R
H
N
S
S
N
R
H
RAFT
controls
VAc, NVP, NVC
RAFT
controls
MMA, MA, St
Scheme 2. RAFT Agent capable of polymerization of both LAMs and MAMs
controlled by pH.
Conclusions
Reversible Addition Fragmentation chain Transfer (RAFT) has emerged
as one of the most important methods for controlling radical
polymerization. RAFT has been shown to be robust and versatile and
applicable to the majority of monomers subject to radical polymer-
ization. However, selection of the appropriate RAFT agent for the
monomers in tandem with the proper reaction conditions is crucial for
successful polymerization.
References
(1) Moad, G.; Rizzardo, E.; Thang, S. H. Aust. J. Chem. 2005, 58, 379-410.
(2) Moad, G.; Rizzardo, E.; Thang, S. H. Aust. J. Chem. 2006, 59, 669-692.
(3) Moad, G.; Rizzardo, E.; Thang, S. H. Polymer 2008, 49, 1079-1131.
(4) Moad, G.; Rizzardo, E.; Thang, S. H. Acc. Chem. Res. 2008, 41, 1133-1142.
(5) Moad, G.; Rizzardo, E.; Thang, S. H. Aust. J. Chem. 2009, 62, 1402-1472.
(6) Moad, G.; Chiefari, J.; Krstina, J.; Postma, A.; Mayadunne, R. T. A.; Rizzardo, E.; Thang,
S. H. Polym. Int. 2000, 49, 993-1001.
(7) Rizzardo, E.; Chiefari, J.; Mayadunne, R. T. A.; Moad, G.; Thang, S. H. ACS Symp. Ser.
2000, 768, 278-96.
(8) Benaglia, M.; Chen, M.; Chong, Y. K.; Moad, G.; Rizzardo, E.; Thang, S. H.
Macromolecules 2009, 42, 9384-9386.
(9) Benaglia, M.; Chiefari, J.; Chong, Y. K.; Moad, G.; Rizzardo, E.; Thang, S. H. J. Am. Chem.
Soc. 2009, 131, 6914-6915.
(10) Moad, G.; Chong, Y. K.; Rizzardo, E.; Postma, A.; Thang, S. H. Polymer 2005, 46,
8458-8468.
(11) Moad, G.; Mayadunne, R. T. A.; Rizzardo, E.; Skidmore, M.; Thang, S. Macromol. Symp.
2003, 192, 1-12.
(12) Chong, Y. K.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 2007, 40, 4446-4455.
(13) Postma, A.; Davis, T. P.; Evans, R. A.; Li, G.; Moad, G.; OShea, M. Macromolecules 2006,
39, 5293-5306.
(14) Postma, A.; Davis, T. P.; Li, G.; Moad, G.; OShea, M. Macromolecules 2006, 39,
5307-5318.
(15) Postma, A.; Davis, T. P.; Moad, G.; OShea, M. S. Macromolecules 2005, 38, (13),
5371-5374.
(16) Chong, B.; Moad, G.; Rizzardo, E.; Skidmore, M.; Thang, S. H. Aust. J. Chem. 2006, 59,
755-762.
(17) Rizzardo, E.; Chen, M.; Chong, B.; Moad, G.; Skidmore, M.; Thang, S. H. Macromol.
Symp. 2007, 248, 104-116.
(18) Chong, Y. K.; Moad, G.; Rizzardo, E.; Skidmore, M. A.; Thang, S. H. Macromolecules
2007, 40, 9262-71.
(19) Thang, S. H.; Chong, Y. K.; Mayadunne, R. T. A.; Moad, G.; Rizzardo, E. Tetrahedron Lett.
1999, 40, 2435-8.
(20) Chong, Y. K.; Krstina, J.; Le, T. P. T.; Moad, G.; Postma, A.; Rizzardo, E.; Thang, S. H.
Macromolecules 2003, 36, (7), 2256-2272.
4
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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RAFT Agents
For a complete description of available RAFT agents, please visit sigma-aldrich.com/poly
Name Structure Description Cat. No.
2-Cyano-2-propyl benzodithioate
S
CN H3C S
CH3
RAFT agent for controlled radical
polymerization; especially suited for
the polymerization of methacrylate
and methacrylamide monomers.
Chain Transfer Agent (CTA)
722987-1G
722987-5G
4-Cyano-4-(phenylcarbono-
thioylthio)pentanoic acid
S
CN H3C S
OH
O
722995-1G
722995-5G
2-Cyano-2-propyl dodecyl
trithiocarbonate CH3(CH2)10CH2
S S
CN H3C S
CH3
RAFT agent for controlled radical
polymerization; especially suited for
the polymerization of methacrylate,
methacrylamide and styrene monomers.
Chain Transfer Agent (CTA)
723037-1G
723037-5G
4-Cyano-4-[(dodecylsulfanylthio-
carbonyl)sulfanyl]pentanoic acid
CH3(CH2)10CH2
S S
CN H3C S
OH
O
723274-1G
723274-5G
2-(Dodecylthiocarbonothioylth-
io)-2-methylpropionic acid CH3(CH2)10CH2
S S
CH3 H3C S
O
OH RAFT agent for controlled radical
polymerization; especially suited for
the polymerization of styrene, acrylate
and acrylamide monomers.
Chain Transfer Agent (CTA)
723010-1G
723010-5G
Cyanomethyl dodecyl
trithiocarbonate
S S CN
S
CH3(CH2)10CH2
723029-1G
723029-5G
Cyanomethyl methyl(phenyl)car-
bamodithioate N S CN
CH3
S
RAFT agent for controlled radical
polymerization; especially suited for
the polymerization of vinyl ester
and vinyl amide monomers.
Chain Transfer Agent (CTA)
723002-1G
723002-5G
Bis(thiobenzoyl) disulfide
S
S
S
S
Precursor for the synthesis of RAFT
agents for controlled radical
polymerization.
723118-5G
Bis(dodecylsulfanylthiocarbonyl)
disulfide CH3(CH2)10CH2
S S
S
S S
CH2(CH2)10CH3
S
723126-5G
Radical Initiators
For a complete list of available radical initiators, please visit sigma-aldrich.com/poly
Name Structure Purity Cat. No.
1,1-Azobis(cyclohexanecarbonitrile),
ACHN
N
N
CN
CN
98% 380210-25G
380210-100G
2,2-Azobis(2-methylpropionamidine)
dihydrochloride,
AAPH
H2N
N
N
NH2
NH
NH CH3 H3C
H3C CH3
2HCl
97% 440914-25G
440914-100G
2,2-Azobis(2-methylpropionitrile),
AIBN
C N
N C N
CH3 H3C
H3C CH3
N
98% 441090-25G
441090-100G
4,4-Azobis(4-cyanovaleric acid),
ACVA HO
N
N
OH
O
O
H3C CN
H3C CN
98.0% 11590-25G
11590-100G
5
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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Methacrylamide Monomers
For a complete list of available acrylamides and methacrylamide monomers, please visit sigma-aldrich.com/acrylic
Name Structure Purity Cat. No.
Methacrylamide
H2C
NH2
O
CH3
98% 109606-5G
109606-250G
109606-500G
N-Isopropylmethacrylamide
H2C
N
H
CH3
CH3 O
CH3
97% 423548-5G
423548-25G
N-[3-(Dimethylamino)propyl]meth-
acrylamide
N N
H
H2C
O
CH3
CH3
CH3
99% 409472-250ML
409472-1L
7-[4-(Trifluoromethyl)coumarin]
methacrylamide
N
H
H2C
O
O O
CF3
CH3
98% 566225-100MG
566225-500MG
Disperse Orange 3 methacrylamide
H2C
CH3
N
H
O
N
N NO2
- 595845-100MG
595845-1G
Methacrylate Monomers
For a complete list of available methacrylate monomers,
please visit sigma-aldrich.com/acrylic
OR
O
H
2
C
CH
3
Monofunctional Methacrylate Monomers
Name R Group Purity Additive Cat. No.
Methacryloyl chloride
Cl
O
H2C
CH3
97% monomethyl ether hydroquinone
200 ppm as stabilizer
523216-100ML
523216-1L
Sodium methacrylate
Na *
99% - 408212-50G
408212-250G
Methacrylic acid
H *
99% monomethyl ether hydroquinone
250 ppm as inhibitor
155721-5G
155721-100G
155721-500G
155721-2KG
155721-3KG
155721-18KG
Methyl methacrylate
CH3 *
99% monomethyl ether hydroquinone
10-100 ppm as inhibitor
M55909-25ML
M55909-500ML
M55909-1L
M55909-2L
M55909-17L
Ethyl methacrylate
CH3 *
99% monomethyl ether hydroquinone
15 ppm as inhibitor
234893-100ML
234893-500ML
234893-1L
2,2,2-Trifluoroethyl meth-
acrylate
CF3 *
99% - 373761-5G
373761-25G
Butyl methacrylate
CH
3
*
99% monomethyl ether hydroquinone
10 ppm as inhibitor
235865-5ML
235865-100ML
235865-1L
235865-18L
Hexyl methacrylate
* CH2(CH2)4CH3
98% - 462373-500G
462373-1KG
Lauryl methacrylate
* CH2(CH2)10CH3
96% - 291811-100ML
291811-500ML
Stearyl methacrylate
* CH
2
(CH
2
)
16
CH
3
- monomethyl ether hydroquinone
300-500 ppm as inhibitor
411442-250ML
411442-1L
6
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Name R Group Purity Additive Cat. No.
tert-Butyl methacrylate CH3
CH3
CH3
*
98% monomethyl ether hydroquinone
200 ppm as inhibitor
463353-100ML
463353-250ML
Isobutyl methacrylate CH3
CH3
*
97% monomethyl ether hydroquinone
15 ppm as inhibitor
169919-1L
169919-18L
2-Ethylhexyl methacry-
late
CH3
CH3
* 98% monomethyl ether hydroquinone
~50 ppm as stabilizer
290807-25ML
290807-1L
2-Hydroxyethyl metha-
crylate
OH
*
99% monomethyl ether hydroquinone
50 ppm as inhibitor
477028-25ML
477028-100ML
2-Hydroxyethyl metha-
crylate
OH
*
97% monomethyl ether hydroquinone
200-220 ppm as inhibitor
128635-5G
128635-500G
128635-1KG
128635-18KG
Hydroxypropyl methacry-
late
OH *
97% monomethyl ether hydroquinone
250-350 ppm as inhibitor
268542-100ML
268542-1L
268542-18L
2-Aminoethyl methacry-
late hydrochloride
NH2
*
HCl 90% - 516155-5G
516155-25G
2-(Dimethylamino)ethyl
methacrylate N
CH3
CH3
*
98% monomethyl ether hydroquinone
2,000 ppm as inhibitor
234907-5ML
234907-100ML
234907-1L
2-(Diethylamino)ethyl
methacrylate
N CH3
CH3
*
99% phenothiazine 100 ppm as inhibitor 408980-250ML
408980-1L
2-Isocyanatoethyl metha-
crylate
NCO
*
98% BHT <0.1% as inhibitor 477060-5ML
477060-50ML
Allyl methacrylate CH
2
*
98% monomethyl ether hydroquinone
50-185 ppm as inhibitor
234931-100ML
234931-500ML
Glycidyl methacrylate
O
* 97% monomethyl ether hydroquinone
100 ppm as inhibitor
151238-100G
151238-500G
Furfuryl methacrylate
O
*
97% monomethyl ether hydroquinone
200 ppm as inhibitor
411760-25ML
411760-100ML
Benzyl methacrylate * 96% monomethyl ether hydroquinone
50 ppm as inhibitor
409448-250ML
409448-1L
Cyclohexyl methacrylate
*
97% monomethyl ether hydroquinone
~60 ppm as inhibitor
408964-100ML
408964-250ML
3-Sulfopropyl methacry-
late potassium salt
S
O
O
OK
*
98% - 251658-100G
251658-500G
Isobornyl methacrylate
*
H3C
CH3
CH3
- MEHQ 150 ppm as inhibitor 392111-100ML
392111-500ML
392111-1L
Glycosyloxyethyl metha-
crylate solution,
5% (w/v) in ethanol
O
O
OH
OH
OH
OH
*
- - 659576-25ML
Ferrocenylmethyl metha-
crylate
*
Fe
95%, NMR Ionol 46 (Raschig GmbH) as inhibitor 700479-1G
2-(Trimethylsilyloxy)ethyl
methacrylate O Si
CH3
CH3
CH3
*
96% - 347485-25G
347485-100G
3-(Trimethoxysilyl)propyl
methacrylate Si
OCH
3
OCH
3
OCH
3
*
98% - 440159-100ML
440159-500ML
7
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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Polyfunctional Methacrylate Monomers
Name R Group Purity Additive Cat. No.
Phosphoric acid
2-hydroxyethyl metha-
crylate ester
O P
O
OR'
OR'
*
R' =
and/or
R' =
H
*
O
CH2
CH3
OH
*
- MEHQ 700-1000 ppm 695890-100ML
695890-250ML
1,4-Butanediol
dimethacrylate
O
O
CH2
CH3
*
95% monomethyl ether hydroquinone
100 ppm as inhibitor
234958-100G
234958-500G
1,6-Hexanediol
dimethacrylate
CH2(CH2)4CH2O
O
CH2
CH3
*
- hydroquinone 100 ppm as inhibitor 411736-25ML
411736-100ML
Glycerol dimethacrylate,
mixture of isomers
OR'
OR'
*
O
CH2
CH3
R' = H or *
85% monomethyl ether hydroquinone
200 ppm as inhibitor
436895-100ML
436895-500ML
Diurethane dimethacry-
late, mixture of isomers
O
H
N
O
CH3
R' CH3
R'
N
H
O
O
O
O
CH2
CH3
*
R' = H or CH3 (~ 1:1)
- topanol 225 ppm 25 ppm as inhibitor 436909-100ML
436909-500ML
Trimethylolpropane
trimethacrylate
* O
CH2
CH3
O
CH3 O
H3C
H2C
O
- monomethyl ether hydroquinone
175 ppm as inhibitor
246840-100G
246840-500G
Materials Science
sigma-aldrich.com
For more information or to request a quote, please contact us at [email protected]
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O
O
CH
3
CH
2
Fe
HS
O
SH
n
8
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Block Copolymer Synthesis Using a Commercially Available
Nitroxide-Mediated Radical Polymerization (NMP) Initiator
Nam S. Lee and Karen L. Wooley*
Departments of Chemistry and Chemical Engineering
Texas A&M University
P.O. Box 30012, 3255 TAMU, College Station, TX 77842-3012
*Email: [email protected]
Introduction
Controlled radical polymerization, which provides exquisite tuning of
macromolecular size, structure, composition and architecture, with
experimental convenience, has become one of the most indispensible
tools for polymer chemists. Its emergence in the mid-1990s has greatly
advanced the fields of nanoscience and nanotechnology, by providing
ready access to complex polymers that serve as building blocks for
functional nanostructures with predictable parameters such as the size,
morphology, regioselective placement of functionalities, etc. This
exceptional polymerization control is due to reversible termination
events that mediate the radical concentration and reactivity. The living
character of this type of polymerization provides an ability to produce
polymers with controlled molecular weight and narrow molecular
weight distribution, and, moreover, to chain extend with different
monomers and obtain multi-block copolymers. Nitroxide-mediated
radical polymerization (NMP) is one of these controlled radical
polymerizations that also includes atom transfer radical polymerization
(ATRP), and reversible addition-fragmentation chain transfer (RAFT)
polymerization. NMP stands out due to its simplicity: the polymerization
is thermally initiated in the absence of an external radical source or a
metal catalyst. As illustrated in Scheme 1, NMP involves a combination
of radical initiator (), monomer (M) and nitroxide radical (R), for trapping
of intermediate radical species. For instance, the thermally-promoted
homolysis of benzoyl peroxide (Aldrich Prod. No. 179981) produces
radicals that are capable of initiating the polymerization of styrene
monomer. Propagation proceeds to produce polymer chains, while
reversible termination events, involving reactions with nitroxide radicals
to afford thermally labile alkoxyamines, mediate the availability of the
reactive radical species and, thereby, provide control over the
polymerization. It is important that the stable nitroxide radicals are
capable of the reversible termination reactions, but do not initiate
polymerizations.
O
O O
O
O
O
initiation
O
O

N O
O
O
O N
nitroxide-trapped alkoxyamine
structure, A
propagation
O
O
N O
reversible
termination
O
O
O N
reversible termination events
provide controlled
polymerization
propagation
propagation to polymer
N O + +
O N
R
5
R
4
R
3
R
1
R
2
thermally labile
alkoxyamine bond
general NMP
initiator structure

M
reversible
termination
R
Scheme 1. Overall mechanism for NMP, illustrated for styrene monomer (M) polymerization initiated by benzoyl peroxide initiator () and mediated by TEMPO nitroxide radicals (R).
Also shown is the general structure for alkoxyamine-based unimolecular NMP initiators.
9
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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One of the most significant advances with NMP was the isolation of an
alkoxyamine that could act as a unimolecular agent, providing both the
reactive, initiating radical and the stable, mediating nitroxide radical.
Initially, nitroxides were employed as additives to reversibly terminate
polymer chains initiated by a separate radical source. By using TEMPO to
trap a styrenyl radical initiated by benzoyl peroxide (as shown by
structure A of Scheme 1), Hawker demonstrated an ability to tune the
molecular weight, define the end groups, and extend to block
copolymers, while maintaining narrow molecular weight distributions.
He later developed a universal initiator, which has received broad
application in laboratories around the world. A key limitation to the use
of this universal initiator remained the challenge of its synthesis. With it
now being offered commercially by Aldrich Materials Science, it is
expected that NMP will experience a renewed vigor of investigation.
With our interest in the construction of nanoscopic objects via the self-
assembly of amphiphilic block copolymers in water, we have used the
universal initiator (Aldrich Prod. No. 700703), in the presence of less
than 5 equivalent percent of the corresponding nitroxide (added to
assist with capping the propagating chain ends during polymerization),
to prepare an amphiphilic diblock copolymer precursor, poly(tert-butyl
acrylate)-b-poly(4-acetoxystyrene) with a controlled molecular weight
and a narrow molecular weight distribution (Scheme 2).
O
N
N
O
O
O O
N
140
N
O
O O
140
O
O
O
N
50
I
II
"Universal initiator"
Aldrich Prod.
No. 700703
Aldrich Prod.
No. 710733
tert-Butyl acrylate
Aldrich Prod.
No. 327182
125 C, 36 h
50% conv.
80% yield
M
n
GPC
= 18.220 Da
M
n
NMR
= 19.130 Da
PDI = 1.10
4-Acetoxystyrene
Aldrich Prod.
No. 380547
125 C, 4 h
25% conv.
87% yield
M
n
GPC
= 26.330 Da
M
n
NMR
= 26.620 Da
PDI = 1.12
Scheme 2. Synthesis of poly(tert-butyl acrylate) (I) continuing on to create poly(t-butyl acrylate)-b-poly(4-acetoxystyrene) (II)
using the universal NMP initiator.
Synthesis of Poly(t-butyl acrylate)
140
(I)
1
H NMR and
13
C NMR spectra were recorded at 300 MHz and 75 MHz,
respectively, as solutions with the solvent proton as a standard. To a
flame-dried 50 mL Schlenk flask equipped with a magnetic stir bar and
under N
2
atmosphere, at room temperature, was added (124 mg,
0.381 mmol, Aldrich Prod. No. 700703), 2,2,5-trimethyl-4-phenyl-3-
azahexane-3-nitroxide (4.19 mg, 0.019 mmol, Aldrich Prod. No. 710733),
and tert-butyl acrylate (10.16 g, 79.6 mmol, Aldrich Prod. No. 327182).
The reaction flask was sealed and stirred for 10 min at rt. The reaction
mixture was degassed through three cycles of freeze-pump-thaw. After
the last cycle, the reaction mixture was recovered back to rt and stirred
for 10 min before being immersed into a pre-heated oil bath at 125 C
to start the polymerization. After 36 h (kinetic data for conversion shown
in Figure 1),
1
H NMR analysis showed 50% monomer conversion had
been reached (Figure 3). The polymerization was quenched by quick
immersion of the reaction flask into liquid N2. The reaction mixture was
dissolved in THF (Aldrich Prod. No. 401757) and precipitated into
H
2
O/MeOH (v:v, 1:4) three times to afford PtBA as a white powder, (4.1 g,
80% yield based upon monomer conversion); M
n
NMR
= 19,130 g/mol,
M
n
GPC
= 18,220 g/mol, PDI = 1.10.
1
H NMR (CD
2
Cl
2
, ppm): 1.43 (br,
1290 H), 1.80 (br, 70 H), 2.21 (br, 160 H), 7.14-7.26 (m, 10 H).
13
C NMR
(CD2Cl2, ppm): 28.4, 36.5, 38.0, 42.5, 80.9, 174.4. The GPC data can be
seen in Figure 2.
Kinetic plot of I
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40
Time (hours)
C
o
n
v
e
r
s
i
o
n

(
p
e
r
c
e
n
t
)
y = 1.9876 + 1.3179x R= 0.99643
Figure 1. Percent conversion of monomers vs. time
GPC trace of I
120
100
80
60
40
20
0
16 18 20 22 24 26
Time (min)
R
I

R
e
s
p
o
n
s
e

(
m
W
)
Figure 2. Molecular weight distribution of I. M
n
= 18,220 g/mol, PDI = 1.10
8 7 6 5 4 3 2 1 0 PPM
Figure 3.
1
H NMR spectrum of I
200 150 100 50 0 PPM
Figure 4.
13
C NMR spectrum of I
10
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Synthesis of Poly(t-butyl acrylate)
140
-b-
poly(acetoxystyrene)
50
(II)
1
H NMR and
13
C NMR spectra were recorded at 300 MHz and 75 MHz,
respectively, as solutions with the solvent proton as a standard. To a
flame-dried 50 mL Schlenk flask equipped with a magnetic stir bar and
under N
2
atmosphere, at room temperature, was added I (124 mg,
0.381 mmol), 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (4.19 mg,
0.019 mmol), and 4-acetoxystyrene (10.16 g, 79.6 mmol, Aldrich Prod.
No. 380547). The reaction flask was sealed and stirred for 10 min at rt.
The reaction mixture was degassed through three cycles of freeze-
pump-thaw. After the last cycle, the reaction mixture was recovered
back to rt and stirred for 10 min before being immersed into a pre-
heated oil bath at 125 C to start the polymerization. After 4 h (kinetic
data for conversion shown in Figure 5),
1
H NMR analysis showed 25%
monomer conversion had been reached (Figure 7). The polymerization
was quenched by quick immersion of the reaction flask into liquid N2.
The reaction mixture was dissolved in THF and precipitated into
H
2
O/MeOH (v:v, 1:4) three times to afford PtBA-b-PAS as a white
powder, (4.62 g, 87% yield based upon monomer conversion);
M
n
NMR
= 26,620 g/mol, M
n
GPC
= 26,330 g/mol, PDI = 1.12.
1
H NMR
(CD2Cl2, ppm): 1.43 (br, 1500 H), 1.80 (br, 100 H), 2.21 (br, 290 H),
6.36-6.82 (m, 190 H), 7.14-7.26 (m, 10 H).
13
C NMR (CD2Cl2, ppm,
Figure 8): 21.5, 28.4, 36.5, 38.0, 40.5, 42.6, 80.9, 121.8, 128.9, 143.0, 149.4,
169.7, 174.7. The GPC data can be seen in Figure 6.
Kinetic plot of II
28
24
20
16
12
8
4
0
0 1 2 3 4 5
Time (hours)
C
o
n
v
e
r
s
i
o
n

(
p
e
r
c
e
n
t
)
y = -0.178 + 6.498x R= 0.99874
Figure 5. Percent conversion of monomers vs. time
GPC trace of II
Time (min)
R
I

R
e
s
p
o
n
s
e

(
m
W
)
160
120
80
40
0
16 18 20 22 24 26
Figure 6. Molecular weight distribution of II. M
n
= 26,330 g/mol, PDI = 1.12
8 7 6 5 4 3 2 1 0 PPM
Figure 7.
1
H NMR spectrum of II
200 150 100 50 0 PPM
Figure 8.
13
C NMR spectrum of II
Normalized GPC Traces
Time (min)
R
I

R
e
s
p
o
n
s
e

(
m
W
)
16 18 20 22 24 26
120
100
80
60
40
20
0
PtBA
PtBA-b-PAS
Figure 9. Normalized GPC traces showing molecular weight distributions of
polymers I and II.
Conclusions
We have demonstrated a facile preparation of an amphiphilic diblock
copolymer precursor with a controlled molecular weight and a low PDI
using the universal NMP initiator (Aldrich Prod. No. 700703). This
required no special apparatus or technique, beyond those employed for
standard radical polymerizations, but only synthesis of the correspond-
ing nitroxide (Aldrich Prod. No. 710733). The final block copolymer was
purified by precipitation to remove excess monomers, and was then
deprotected. The morphology and size of the subsequent supra-
molecularly assembled nanostructures in water depend on the polymer
block length and the ratio of the block lengths, each carefully
manipulated through monomer conversions, the control over which
arises from the universal NMP initiator. With the simplicity of this system,
it is expected that NMP will experience a dramatic increase in breadth
of application.
11
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Acknowledgments
This material is based upon work supported by the National Heart
Lung and Blood Institute of the National Institutes of Health as a
Program of Excellence in Nanotechnology (HL080729). N. S. Lee thanks
GlaxoSmithKline for their financial support through the ACS Division of
Organic Chemistry Graduate Fellowship 20082009.
References
(1) Hawker, C. J. J. Am. Chem. Soc. 1994, 116, 11185.
(2) Moad, G.; Solomon, D. H.; Johns, S. R.; Willing, R. I. Macromolecules 1982, 15, 909;
Rizzardo, E. Chem. Aust. 1987, 54, 32; Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.;
Hamer, G. K. Macromolecules 1993, 26, 2987.
(3) Benoit, D.; Chaplinski, V.; Braslau, R.; Hawker, C. J. J. Am. Chem. Soc. 1999, 121, 3904.
(4) Lee, N. S.; Li, Y.; Ruda, C. M.; Wooley, K. L. Chem. Commun. 2008, 42, 5339.
NMP Initiators
For a complete description of available free radical initiators, please visit sigma-aldrich.com/poly
Name Structure Description Cat. No.
N-tert-Butyl-N-(2-methyl-1-
phenylpropyl)-O-(1-phenylethyl)
hydroxylamine
O
N
t-Bu CH3
CH3 H3C
Universal alkoxyamine initiator for
nitroxide-mediated living radical
polymerization (NMP initiator). Particularly
useful for synthesis of styrene and acrylate
polymers and co-polymers.
700703-250MG
700703-1G
N-tert-Butyl-O-[1-[4-(chlorometh-
yl)phenyl]ethyl]-N-(2-methyl-1-
phenylpropyl)hydroxylamine
O
CH3
N
t-Bu
CH3 H3C
Cl
Functional alkoxyamine initiator for
nitroxide-mediated living radical
polymerization (NMP initiator). Particularly
useful for synthesis of styrene and acrylate
polymers and co-polymers.
711268-250MG
2,2,5-Trimethyl-4-phenyl-3-
azahexane-3-nitroxide
CH3
CH3
CH3
N
O CH3
H3C
Stable nitroxide radical useful in
controlling living radical polymerizations
710733-250MG
710733-1G
TEMPO, 2,2,6,6-Tetramethyl-1-
piperidinyloxy
N H3C
H3C
CH3
CH3
O
Stable nitroxide radical useful in
controlling living polymerizations
426369-1G
426369-5G
Vinyl Amide and Vinyl Ester Monomers
For a complete list of available vinyl monomers, please visit sigma-aldrich.com/monomers
Name Structure Purity Additive Cat. No.
N-Vinylformamide
N
H
H
O
CH2
98% 4-Hydroxy-TEMPO 25-55 ppm
as stabilizer
447331-100ML
447331-500ML
N-Methyl-N-vinylacetamide
H3C N
O
CH3
CH2
98% - 255130-100ML
255130-500ML
Vinyl propionate
O
O
H3C
CH2
98% monomethyl ether hydroquinone
<100 ppm as inhibitor
401714-500ML
Vinyl pivalate
t-Bu O CH2
O 99% monomethyl ether hydroquinone
6-15 ppm as stabilizer
124400-250ML
124400-1L
Vinyl neodecanoate, mixture
of isomers
C9H19 O CH2
O - monomethyl ether hydroquinone
5 ppm as inhibitor
134481-1L
Vinyl decanoate
CH3(CH2)7CH2
O
O CH2
95% - 411795-10G
Vinyl stearate
CH3(CH2)15CH2
O
O CH2
95% - 436208-50G
436208-250G
Vinyl chloroformate
Cl O CH2
O 99% BHT 100 ppm as inhibitor 528064-5ML
528064-10ML
Vinyl benzoate
O CH2
O 99% hydroquinone 20 ppm as stabilizer 403091-100ML
403091-500ML
12
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Styrene Monomers
For a complete list of available styrene, functionalized styrere, and substituted styrene monomers, please visit sigma-aldrich.com/monomers
Functionalized Styrene Monomers
Name Structure Purity Additive Cat. No.
-Bromostyrene
CH2
Br 90% - 292273-5G
292273-25G
2-Bromostyrene
CH2
Br
97% - 132683-1G
132683-5G
3-Bromostyrene
CH2
Br 97% 3,5-di-tert-butylcatechol 0.1%
as inhibitor
132675-1G
132675-5G
4-Bromostyrene
Br
CH2
98% 3,5-di-tert-butylcatechol 0.1%
as inhibitor
124141-10G
124141-25G
2-Chlorostyrene
Cl
CH2
97% hydroquinone 0.1% as stabilizer 160679-5G
160679-25G
3-Chlorostyrene
CH2
Cl
98% 3,5-di-tert-butylcatechol 0.1%
as stabilizer
C71009-1G
4-Chlorostyrene
Cl
CH2
97% 4-tert-butylcatechol 500 ppm
as inhibitor
C71203-10G
C71203-50G
4-Chloro--methylstyrene
CH2
Cl
CH3 98% tert-butylcatechol 100 ppm
as stabilizer
C57200-25G
2,6-Dichlorostyrene
CH2
Cl
Cl 99% - D74509-2.5G
D74509-10G
4-Vinylbenzyl chloride
CH2
Cl
90% tert-butylcatechol 500 ppm
as inhibitor
nitroparaffin 500 ppm as inhibitor
436887-25ML
436887-100ML
Vinylbenzyl chloride
Cl
CH2 CH2
Cl
Mixture of isomers
97% tert-butylcatechol 50-100 ppm
as inhibitor
nitromethane 700-1100 ppm
as inhibitor
338729-25G
338729-100G
2-Isopropenylaniline
CH
2
CH
3
NH2
98% - 194212-5G
194212-25G
3-Vinylaniline
CH
2
NH
2
97% - 560839-1G
560839-5G
4-Vinylaniline
CH
2
H
2
N
97% - 536180-1G
536180-5G
N,N-Dimethylvinylbenzyl-
amine, mixture of isomers CH2
N
H3C
CH3 97% - 476382-1G
476382-10G
3-Vinylbenzoic acid CH2
OH O
96% - 523089-5G
4-Vinylbenzoic acid
CH2
HO
O
97% - 254738-1G
254738-5G
3-Isopropenyl-,-dimethyl-
benzyl isocyanate
CH
2
CH
3
NCO
H
3
C
H
3
C
95% - 361771-250ML
361771-1L
13
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Materials Science
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Substituted Styrene Monomers
Name Structure Purity Additive Cat. No.
-Methylstyrene
CH2
CH3 99% p-tert-butylcatechol 15 ppm
as inhibitor
M80903-5ML
M80903-100ML
M80903-1L
Methylstyrene
CH2
CH3
99% 4-tert-butylcatechol 50 ppm
as stabilizer
522864-250ML
522864-1L
3-Methylstyrene
CH2
CH3
99% 3,5-di-tert-butylcatechol 0.1%
as inhibitor
184675-5G
4-Methylstyrene
CH2
H3C
96% 3,5-di-tert-butylcatechol
as inhibitor
M80806-10ML
M80806-100ML
M80806-500ML
1,3-Diisopropenylbenzene CH3
CH2
CH2
H3C
97% - 255173-250ML
255173-1L
2,4-Dimethylstyrene
CH2
CH3 H3C
97% tert-butylcatechol 100 ppm
as inhibitor
262633-5G
2,5-Dimethylstyrene
CH2
CH3
H3C 99% - 361135-1G
361135-5G
2,4,6-Trimethylstyrene
CH2
CH3
CH3
H3C
95% tert-butylcatechol <0.05%
as inhibitor
259780-5G
4-tert-Butylstyrene
CH2
H3C
H3C
CH3
93% tert-butylcatechol 100 ppm
as inhibitor
523933-250ML
523933-1L
4-Vinylanisole
CH2
H3CO
97% - 141003-5G
141003-25G
4-Acetoxystyrene
CH2
O
O
H3C
96% MEHQ 200-300 ppm as inhibitor 380547-5ML
380547-25ML
4-tert-Butoxystyrene
CH2
O
CH3
CH3
H3C
99% 4-tert-butylcatechol 200 ppm
as inhibitor
455644-10ML
455644-50ML
3,4-Dimethoxystyrene
H3CO
CH2
OCH3
- hydroquinone 1% as inhibitor 154466-5G
154466-10G
2-Fluorostyrene
CH2
F
98% - 290505-5G
3-Fluorostyrene
CH2
F
97% - 219452-1G
219452-5G
4-Fluorostyrene
F
CH2
99% tert-butylcatechol as inhibitor 155799-1G
155799-10G
2-(Trifluoromethyl)styrene
CH2
CF3
99% 4-tert-butylcatechol 0.1%
as inhibitor
369594-1G
3-(Trifluoromethyl)styrene
CF3
CH2
99% 4-tert-butylcatechol as inhibitor 366692-1G
4-(Trifluoromethyl)styrene
F3C
CH2
98% 4-tert-butylcatechol 0.1%
as inhibitor
369608-1G
2,6-Difluorostyrene F
F
CH2
99% 4-tert-butylcatechol 0.25%
as inhibitor
374407-250MG
374407-1G
14
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Name Structure Purity Additive Cat. No.
2,3,4,5,6-Pentafluorostyrene
CH2
F
F
F
F F
99% p-tert-butylcatechol 0.1%
as inhibitor
196916-25G
3-Nitrostyrene
CH2
NO2
96% - N26601-2.5G
N26601-10G
(Vinylbenzyl)trimethylammo-
nium chloride
CH2
N
CH3
CH3
H3C
Cl
99% - 458694-100G
458694-250G
2-Vinylnaphthalene
CH2
98% - 453870-1G
2-Vinylnaphthalene
CH2
95% - V2909-5G
V2909-25G
4-Vinylbiphenyl
CH2
- - V1805-1G
V1805-10G
9-Vinylanthracene CH2 97% - V1708-1G
V1708-5G
Materials Science
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15
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ATRP for Everyone: Ligands and Initiators for the
Clean Synthesis of Functional Polymers
Wojciech Jakubowski, Nicolay V. Tsarevsky, Patrick McCarthy*,
Krzysztof Matyjaszewski
ATRP Solutions, Inc.
166N. Dithridge Street, Suite G4, Pittsburgh, PA 15213
*Email: [email protected]
Introduction
Atom transfer radical polymerization (ATRP)
1-4
has emerged as one of
the most successful synthetic techniques for the preparation of
polymers with predetermined molecular weights, narrow molecular
weight distributions, and high degrees of chain end functionalities
(Scheme 1). The unprecedented control over molecular architecture
afforded by the ATRP enables preparation of systematic polymer
libraries.
5
Scheme 1 exemplifies a systematic library of star-shaped
polymers, where the polymers in each row have the same arm size and
those in each column have the same number of arms. Such libraries can
provide important data for understanding the relationships between
polymer structure and physical properties or function.
R( R
R
variable materials
library
R
H
X
X
R R
X)
n
+ +
+
+
Mt
Z
/L Mt
Z+1
/L
Mt
Z+1
/L
M
I-X
Ox
Red
or
AIBN
I
k
act
k
deact
k
t
k
p
R
[M]
0
/ [R(X)
n
]
0
n
ICAR ATRP ARGET ATRP
( (
Scheme 1. Schematic illustration of the ATRP (top) and an example of a star-shaped
polymer library.
Catalysts for ATRP
ATRP is catalytic process using a metal complex, in which the transition
metal Mt can exist in two different oxidation states. The lower oxidation
state metal complex Mt
z
/L (L is a ligand) reacts with the ATRP initiator
(alkyl halide RX) to yield a radical R

and the corresponding higher

oxidation state metal complex with a coordinated halide anion
X-Mt
z+1
/L, in a process termed activation, proceeding with the rate
constant, kact. The latter complex can transfer the halogen atom back to
the radical, re-generating the alkyl halide and the lower oxidation state
metal complex. The radicals can react with the monomer M (generating
polymer with the rate constant of propagation k
p
), with each other
(termination with the rate constant, kt) or with X-Mt
z+1
/L (deactivation
with the rate constant, k
deact
). The last step, which distinguishes ATRP
from conventional radical polymerization, yields the halogen-terminated
polymeric dormant state, which can be reactivated in a reaction with
Mt
z
/L. If the deactivation process is efficient (i.e., high value of kdeact) and
if all polymer chains are initiated within a short period by appropriate
selection of the alkyl halide initiator, the resulting polymer will be
characterized by a narrow molecular weight distribution. Additionally, it
is desirable to use an active catalyst with a high value of the ratio of
k
act / kdeact, termed the ATRP equilibrium constant, kATRP, to ensure fast
polymerization. The rate constants kact and kdeact depend on both the
transition metal and the ligand. Rules for the rational selection of active
catalysts for ATRP for various reaction media and monomers have
been developed.
2, 6
Various metals and ligands have been successfully employed as catalysts
in ATRP, but the most often used are the catalysts based on copper (the
two oxidation states are Cu
I
and Cu
II
) and N-containing ligands. One
drawback of the classical ATRP is the use of high amounts of the
catalyst.
4
The obtained polymers are well-defined in terms of molecular
weight distribution and chain-end functionality but require tedious
purification to remove the catalyst. Although various methods for
catalyst removal have been developed,
2, 7
the extra purification step is
associated with longer time needed to obtain the final product, and
with generation of waste, both of which increased the cost of the
materials prepared by ATRP. However, the use of ligands such as tris[2-
(dimethylamino)ethyl]amine (Me
6
TREN, Aldrich Prod. No. 723142) and
tris(2-pyridylmethyl)amine (TPMA, Aldrich Prod. No. 723134) alleviates
this problem (Figure 1). These ligands can be used in new techniques
called Activators ReGenerated by Electron Transfer (ARGET)
8, 9
and
Initiators for Continuous Activator Regeneration (ICAR)
10
which allow to
decrease amount of catalyst to only few, often single-digit, ppm. For
comparison, 1,000 to 10,000 ppm were used in traditional ATRP. For
many applications, in these new systems the residual copper can be left
in the final colorless products. Both techniques employ a reducing
agent: a radical initiator such as AIBN in ICAR ATRP;
10
and tin(II)
ethylhexanoate
8, 9, 11-13
(Aldrich Prod. No. S3252), ascorbic acid,
14
glucose,
9
hydrazine,
10
or Cu(0)
15
in ARGET ATRP. These reducing agents
allow for regeneration of the lower oxidation state metal complex,
which would normally be irreversibly converted to the higher oxidation
state complex due to radical termination by a process dubbed
"persistent radical effect".
16
N
N
N N
N
N
N
N
Me
6
TREN
Aldrich Prod.
No. 723142
TPMA
Aldrich Prod.
No. 723134
Figure 1. Ligands for Cu-mediated ATRP using ppm amounts of catalyst.
16
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R
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The ARGET and ICAR ATRP processes allow chemists to reduce the
amount of catalyst more than one thousand times and the polymers
obtained are white or colorless. These processes also allow preparation
of well-defined block copolymers,
12
polymers with high molecular
weight,
11, 17
high chain-end functionality
11
and adjustable molecular
weight distribution.
18
In addition, since the level of control in an ARGET
and ICAR ATRP is only weakly affected by an excess of reducing agent,
the reaction can be successfully carried out in the presence of limited
amounts of air.
13
Reactions can be carried out without deoxygenation, in
flasks fitted with rubber septa or even in simple jars. This was
demonstrated in our laboratory by placing functionalized wafers in one
of these vessels and growing very dense polymer brushes
(~0.4 chain/nm
2
), including block copolymer brushes, without any
deoxygenation. ATRP stops after opening the vessel to air but starts
again when a sufficient amount of reducing agent is added to the
closed flask. This polymerization process does not require any special
skills and is especially well-suited for grafting from larger surfaces, but
can also be applied for preparation of any other polymer materials. Only
very active catalysts derived from Me
6
TREN and TPMA can be used in
these new techniques. Figure 2 presents the kinetic plot, evolution of
molecular weights and polydispersities with conversion and GPC traces
for polymerization of styrene (St) with 50 ppm of Cu
II
Br
2
/TPMA catalyst
in the presence of AIBN as reducing agent. Molecular weight control is
excellent and follows theoretical values based on quantitative initiation.
The polymer, after precipitation in hexane, appeared as a white solid
powder containing only 5 ppm of the residual catalyst. If more Cu
removal is needed, the ATRP pure

resin can be used.

5, 19
Typical ICAR ATRP procedure
The following is a procedure employing very low concentration of
copper catalyst that yields well-defined polystyrene macroinitiator
(PSt-Br) with degree of polymerization 100. As shown in Figure 2,
the polymerization is well-controlled: the linear first order kinetic plot of
monomer consumption indicates constant number of active species
and the increase of molecular weights with conversion is characteristic
of a living process. Moreover, the obtained polymer was virtually
colorless without the use of any special purification methods other than
simple precipitation in hexane.
Add CuBr2 (7.8 mg, 3.5 10
-2
mmol) and TPMA (10.1 mg, 3.49
10
-2
mmol) to a 10 mL flask equipped with magnetic stirring bar.
Add DMF (4 mL) to solubilize CuBr
2
/TPMA. Stir for 10 min to
obtain a homogeneous yellowish solution.
Add St (80.0 ml, 0.698 mmol), AIBN (0.153 g, 0.0931 mmol) and ethyl
2-bromoisobutyrate (0.68 mL, 4.65 mmol) to a 200-mL round bottom
flask equipped with a magnetic stirring bar.
Transfer the catalyst solution to the 200 mL round bottom flask
reactor.
Close the flask reactor with glass adapter (with glass stopcock and a
rubber septum). Stir the solution while purging with nitrogen for 1 h.
Place the flask in an oil bath at 70
o
C. To follow the progress of the
reaction, samples can be withdrawn with a stainless steel needle. The
samples can be analyzed by GC or NMR (monomer conversion) and
SEC (molecular weight and polydispersity).
After 20.5 h*, the monomer conversion reaches 69 %. M
n
=
9,700 g/mol, PDI = 1.11. The reactor is opened to air and allowed
to cool to room temperature.
Dilute the polymer with THF (100 mL) and precipitate into 2 L of
hexane.
Dry the produced polymer at 45
o
C to constant weight (ca. 24 h).
* Time of the reaction may vary depending on a type of used
equipment and purity of chemical reagents.
Polymerization conditions for ICAR ATRP of styrene:
[St]
0
/ [EtBiB]
0
/ [CuBr
2
]
0
/ [TPMA]
0
/ [AIBN]
0
100 / 1 / 0.005 / 0.005 / 0.2
T = 70 C ; DMF as internal standard (5 vol% versus St)
Time [min]
Molecular weight [g/mol]
Conversion of St Time [min]
2.0
1.6
1.2
0.8
0.4
0.0
0.0 0.2 0.4 0.6 0.8 1.0
1.0
1.2
1.4
1.6
1.8
2.0
0.0
2.0x10
3
4.0x10
3
6.0x10
3
8.0x10
3
1.0x10
4
0 400
10
2
10
3
10
4
800 1200
M
o
l
e
c
u
l
a
r

w
e
i
g
h
t

[
g
/
m
o
l
]
L
n
(
[
M
]
0
/
[
M
]
)
P
D
I
t=1.3 h
t=2.5 h
t=5.0 h
t=10.0 h
t=21.0 h
A B
C
D
Figure 2. ICAR ATRP of styrene (St) using 50 ppm of catalyst. (a) Kinetic plot (b) Molecular weight and polydispersity as a function of conversion
(c) Evolution of GPC traces (d) Photograph of polymer after precipitation in hexane
17
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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It is interesting to compare the results of ICAR ATRP employing Me6TREN
or TPMA with the process under similar conditions but with other
catalysts, derived from ligands, such as the traditionally used derivatives
of 2,2-bipyridine (bpy) (ex., Aldrich Prod. No. 482250) or N,N,N,N,N-
pentamethyldiethylenetriamine (PMDETA, Aldrich Prod. No. 369497).
As seen from Table 1, only the polymerizations mediated by the
complexes of Me6TREN and TPMA (the first two entries) were well-
controlled and yielded polymers with narrow molecular weight
distribution.
10
In all cases, only 50 ppm of Cu was employed.
Table 1. ICAR ATRP of St initiated by ethyl 2-bromoisobutyrate (EBiB) in the presence of various Cu-based catalysts.
St / EBiB / CU
II
/ AIBN
(60 C, in anisole, (50 vol % vs. St)) Ligand
Cu
(ppm)
Time
(min)
Conv.
(%)
M
n
(theor.)
M
n
(SEC) PDI
200/1/0.01/0.1
Me
6
TREN
0.01
N
N N
N
50 2760 44 8700 7900 1.12
200/1/0.01/0.1
TPMA
0.01
N
N N
N
50 2880 39 7800 6800 1.09
200/1/0.01/0.1
PMDETA
0.01
N
N N
50 2880 29 5600 4500 1.62
200/1/0.01/0.1
dNbpy
0.02
N N
C9H19 C9H19
50 2940 36 7200 5600 1.68
Me
6
TREN and TPMA were successfully used in ICAR and ARGET ATRP of
various monomers such as styrene,
9-11
methyl acrylate,
15
butyl acrylate,
8
methyl methacrylate,
8, 12
butyl methacrylate,
20
dimethylaminoethyl
methacrylate
21
and acrylonitrile.
17, 22
They can also be used in classical
ATRP of coordinating monomers such as, for example, 4-vinylpyridine
(Aldrich Prod. No. V3204). Rate of ICAR ATRP is not affected by the
catalysts but it is defined by the rate of decomposition of the radical
initiator and can be significantly accelerated at higher temperatures.
Block Copolymers
Block copolymers continue to remain a subject of intense research and
technological interest due to their unusual and useful properties.
23, 24
Current and potential high-technology applications of block copolymers
are based on their ability to self-assemble, in bulk as well as in selective
solvents, into ordered nanostructures. For example, block copolymers
with hydrophilic and hydrophobic segments self-assemble, both in the
solid state and in the solution, to generate a variety of nano-scale
structures. The structures range from simple micellar or lamellar to
complex gyroid. Recent studies on block copolymer self assembly
demonstrated that nano-scale morphology is highly dependent on
block chain length, chain length ratios, polydispersity index, and block
composition. Therefore, it is essential to precisely control the degree of
polymerization of each segment in the block copolymer and achieve
narrow molecular weight distribution. ATRP is a convenient technique
for preparation of block copolymers because the growing polymer chain
contains a stable halogen terminated -end that can act as an initiator
for chain extension.
Figure 3 presents GPC traces of polystyrene-b-poly(t-butyl acrylate) (PSt-
b-PtBA) as an example of synthesis of a block copolymer library.
5
In
order to synthesize these copolymers ICAR and ARGET ATRP were used
with similar conditions as described above. This library can be then
converted to polymeric surfactants polystyrene-b-poly(acrylic acid) (PSt-
b-PAA) by deprotection of t-butyl groups. PSt-b-PAA copolymers may be
used as polymeric surfactants in many applications such as particle
dispersants (organic, inorganic and metals), nano-device delivery
vehicles, blend compatibilizers, coatings, surface modifiers, detergents,
and emulsifiers. The broad range of compositions and molecular
weights provided by each polymeric library synthesized by ATRP allows
rapid screening and identification of the optimal structure for the
particular application. Several systematic polymeric libraries are now
commercially available.
19
PSt-b-PtBA
Molecular weight [g/mol]
A
10
3
10
1
10
5
A
M
n
[g/mol]
6,800
11,800
30,200
1.16
1.14
1.12
12
47
180
DPI
PBA
PDI B
B
C
C
PSt-b-PtBA
PSt
M
n
=5,200 g/mol
PDI=1.11
DP
PSt
=50
G
P
C

s
i
g
n
a
l
Figure 3. GPC traces and properties of PSt-b-PtBA block copolymer library.
18
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Initiators for ATRP
ATRP uses simple initiators, mainly alkyl halides R-X (X = Cl, Br).
1, 25, 26
The
number-average molecular weight Mn of polymers prepared by ATRP
depends on the initial concentration ratio of monomer (M) to initiator as
well as the monomer conversion:
M
n = ([M]0 / [RX]0) Conv MW(M)
where [M]
0
is the initial monomer concentration, [RX]
0
is the initial
concentration of alkyl halide, Conv is the monomer conversion, and
MW(M) is the molecular weight of the monomer. The alkyl halides used
as initiators can contain either one or numerous halogen atoms.
Depending on the exact initiator structure and the number of halogen
atoms, the architecture of the prepared polymers can be varied from
linear (using alkyl halides with a single halogen atom), to star-like or
brush-like (multiple halogen atoms in the initiator). Star polymers can be
generated using initiators with alkyl halide groups attached to a single
core (Figure 4), whereas to obtain brush polymers, the halide
groups should be attached along the backbone of a polymer or
a large molecule or nanoparticle with a high aspect ratio
(e.g., a carbon nanotube).
O
O
O
O
O O
Br
Br
Br
Trifunctional initiator
Aldrich Prod. No. 723185
O
O
O
O
O
O
O
O
Br
Br
Br
Br
Tetrafunctional initiator
Aldrich Prod. No. 723193
O
O O O
O
O
O
Br
O
Br
Br
O
O
Br
O
Br
O
O
Br
Hexafunctional initiator
Aldrich Prod. No. 723207
O
O
O
Br
O
Br
Difunctional initiator
Aldrich Prod. No. 723177
Figure 4. Examples of ATRP initiators yielding polymeric stars.
Four major strategies exist for the synthesis of polymers with functional
groups via ATRP: i) direct polymerization of functional monomers, ii)
polymerization of "protected" monomers followed by post-polymer-
ization chemical transformations, iii) the use of functional initiators, and
iv) substitutions of the terminal halogen atom. The first two approaches
yield polymers with multiple functionalities along the backbone
whereas the last two yield end-functionalized polymers. Figure 5
illustrates structures of alkyl halide functional initiators that yield end-
functionalized polymers. Groups such as hydroxy are suitable for the
synthesis of polymers that can react with molecules, or surfaces with
carboxylic acid groups. Allyl group-containing initiators yield polymers
that can participate in hydrosilylation or ene reactions with polymers or
surfaces containing Si-H or S-H bonds, respectively. Trichlorosilyl groups
react with surfaces containing hydroxy or amine groups (including
Si-OH bonds), such as those on the surface of silica particles or glass.
Finally, disulfide-containing difunctional initiators yield polymers con-
taining a functional group able to react with gold surfaces, and also
gives the polymers the ability to degrade in reducing environments.
O
S
S
O
Br
O
O
Br
HO
O
Br
O
Hydroxy initiator
Aldrich Prod. No. 723150
Biodegradable (disulfde) initiator
Aldrich Prod. No. 723169
O
Br
O
9
O
Br
O
11
O
Br
O
17
Allyl initiator
Aldrich Prod. No. 723215
Dodecyl initiator
Aldrich Prod. No. 723223
Stearyl initiator
Aldrich Prod. No. 723231
Figure 5. Examples of ATRP initiators that can be used to prepare end-functionalized
and disulfide containing polymers.
Monomer M: styrene, acrylate,
methacrylate type
FG
Br
Br
Br
S
S
FG: hydroxyl group
- modifcation of chain-end by reaction
of small molecules with OH group
- ring opening polymerization using OH
group as initiating site
Br: bromine group
- extension with second
type of monomer
using ATRP
Br: bromine group
- extension with
second type of
monomer using
ATRP
Br: bromine group
- extension with
second type of
monomer using
ATRP
FG: disulfde group
- degradation of
polymer upon
reducing
environment
Figure 6. Examples of end-functionalized polymers prepared by ATRP using an
initiator with a hydroxy or disulfide functional group (FG).
A much broader variety of functional alkyl halides can be easily
custom-synthesized.
1
Several concepts for functional polymer architec-
tures that can be prepared using functionalized ATRP initiators are
further illustrated in Figure 6. It should be emphasized that the
polymers prepared by ATRP contain two chain ends: the -end (FG)
derived from the initiator and the -end, which is normally a bromine or
chlorine atom. Alkyl halides can participate in a number of nucleophilic
substitution reactions, which expands significantly the types of end-
functional polymers accessible through ATRP.
25
19
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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Summary
The number of materials and commercial products that use polymers
either in a pure form or as a part of more complex mixtures, blends, and
composites, is countless. The properties and application of polymers
depend not only on the molecular size but also on the molecular shape
and composition.
27
Today, ATRP is one of the most powerful polymer
synthetic methods which allows control over molecular architecture, as
evidenced by over one hundred patent applications, over a thousand
journal articles published annually, and also in a number of commercial
products made in US, Japan and Europe. Due to recent advancements in
initiation processes (ARGET and ICAR ATRP) it is relatively easy to
perform any polymerization reaction and the purification of the final
products is now easier, while generating a minimum amount of waste.
References
(1) Matyjaszewski, K.; Tsarevsky, N. V. Nat. Chem. 2009, 1, 276-288.
(2) Tsarevsky Nicolay, V.; Matyjaszewski, K. Chem Rev 2007, 107, 2270-99.
(3) Matyjaszewski, K.; Xia, J. Chem. Rev. 2001, 101, 2921-2990.
(4) Wang, J.-S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614-15.
(5) Jakubowski, W.; Tsarevsky, N. V.; McCarthy, P. ACS Symp. Ser. 2009, 1023, 343-355.
(6) Tsarevsky, N. V.; Tang, W.; Brooks, S. J.; Matyjaszewski, K. ACS Symp. Ser. 2006,
944, 56-70.
(7) Tsarevsky, N. V.; Matyjaszewski, K. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 5098.
(8) Jakubowski, W.; Matyjaszewski, K. Angew. Chem., Int. Ed. 2006, 45, 4482-4486.
(9) Jakubowski, W.; Min, K.; Matyjaszewski, K. Macromolecules 2006, 39, 39-45.
(10) Matyjaszewski, K.; Jakubowski, W.; Min, K.; Tang, W.; Huang, J.; Braunecker, W. A.;
Tsarevsky, N. V. Proc. Natl. Acad. Sci. 2006, 103, 15309-15314.
(11) Jakubowski, W.; Kirci-Denizli, B.; Gil, R. R.; Matyjaszewski, K. Macromol. Chem. Phys.
2008, 209, 32-39.
(12) Mueller, L.; Jakubowski, W.; Tang, W.; Matyjaszewski, K. Macromolecules 2007, 40,
6464-6472.
(13) Matyjaszewski, K.; Dong, H.; Jakubowski, W.; Pietrasik, J.; Kusumo, A. Langmuir 2007,
23, 4528-4531.
(14) Min, K.; Gao, H.; Matyjaszewski, K. Macromolecules 2007, 40, 1789-1791.
(15) Matyjaszewski, K.; Tsarevsky, N. V.; Braunecker, W. A.; Dong, H.; Huang, J.; Jakubowski,
W.; Kwak, Y.; Nicolay, R.; Tang, W.; Yoon, J. A. Macromolecules 2007, 40, 7795-7806.
(16) Fischer, H. Macromolecules 1997, 30, 5666-5672.
(17) Dong, H.; Tang, W.; Matyjaszewski, K. Macromolecules 2007, 40, 2974-2977.
(18) Listak, J.; Jakubowski, W.; Mueller, L.; Plichta, A.; Matyjaszewski, K.; Bockstaller, M. R.
Macromolecules 2008, 41, 5919-5927.
(19) www.atrpsolutions.com
(20) Chan, N.; Cunningham, M. F.; Hutchinson, R. A. Macromol. Chem. Phys. 2008, 209,
1797-1805.
(21) Dong, H.; Matyjaszewski, K. Macromolecules 2008, 41, 6868-6870.
(22) Pietrasik, J.; Dong, H.; Matyjaszewski, K. Macromolecules 2006, 39, 3914-3920.
(23) Hadjichristidis, N.; Pispas, S.; Floudas, G., Block Copolymers: Synthetic Strategies,
Physical Properties, and Applications. John Wiley & Sons, Inc.: Hoboken, 2003.
(24) Hamley, I. W., Development in Block Copolymer Science and Technology. John Wiley &
Sons, 2004.
(25) Coessens, V.; Pintauer, T.; Matyjaszewski, K. Prog. Polym. Sci. 2001, 26, 337-377.
(26) Ouchi, M.; Terashima, T.; Sawamoto, M. Chem. Rev. 2009, 109, 4963-5050.
(27) Matyjaszewski, K.; Gnanou, Y.; Leibler, L., Macromolecular Engineering. Precise
Synthesis, Materials Properties, Applications. Wiley-VCH: Weinheim, 2007.
Ligands for ATRP
Name Structure Cat. No.
Tris(2-pyridylmethyl)amine,
TPMA
N
N
N
N
723134-250MG
723134-1G
Tris[2-(dimethylamino)ethyl]amine,
Me
6
TREN
N
N
N
CH3
CH3
CH3
H3C
N
CH3
H3C 723142-1ML
4,4-Dinonyl-2,2-dipyridyl,
dNbpy
N N
CH3(CH2)7CH2 CH2(CH2)7CH3
482250-1G
482250-5G
N,N,N,N,N-Pentamethyldiethylenetriamine,
PMDETA
N
N N
CH3
CH3
H3C CH3
CH3
369497-250ML
369497-1L
20
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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ATRP Initiators
For a complete description of available ATRP initiators including purities, please visit sigma-aldrich.com/poly
Name Structure Description Cat. No.
2-Hydroxyethyl 2-bromoi-
sobutyrate
O
OH
O
Br
H3C
CH3
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of hydroxy functionalized
telechelic polymers. Can be used to modify
carboxylate- or isocyanate- modified surfaces,
particles or biomolecules.
723150-1G
723150-5G
Ethylene bis(2-bromoiso-
butyrate) O
O
O
O
Br
H3C
H3C
Br
CH3
CH3
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of difunctional polymers.
723177-1G
723177-5G
1,1,1-Tris(2-bromoisobu-
tyryloxymethyl)ethane
O
CH3
O
CH3
H3C
Br
O O
CH3 H3C
Br
O
O
Br
CH3
CH3
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of trifunctional polymers.
723185-1G
723185-5G
Pentaerythritol tetrakis(2-
bromoisobutyrate)
O
O
O
O
H3C
CH3
Br
Br
CH3
CH3
O
O
CH3
CH3
Br
O
O
H3C
Br
CH3
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of tetrafunctional polymers.
723193-1G
723193-5G
Dipentaerythritol hexakis
(2-bromoisobutyrate)
O
O
O
O
Br
H3C
CH3
Br
CH3
H3C
O
O
CH3
CH3
Br
O
O
O
O
Br
CH3
CH3
Br
CH3
CH3
O
O
H3C
CH3
Br
O
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of hexafunctional polymers.
723207-1G
723207-5G
Bis[2-(2-bromoisobutyry-
loxy)ethyl]disulfide
S
O
O
Br
CH3
S
O
O
Br
H3C
CH3
CH3 Atom Transfer Radical Polymerization (ATRP)
initiator for the preparation of biodegradable
polymers as well as polymers that adhere to
gold surfaces.
723169-1G
723169-5G
10-Undecenyl 2-bromoi-
sobutyrate
O
O
Br
H3C
CH3
CH2(CH2)7CH2CH=CH2
Atom Transfer Radical Polymerization (ATRP)
initiator that reacts with surfaces containing
S-H bonds. Precursor of various silane-containing
polymers and initiators. Hydrosilation with Cl3SiH
yields an initiator that reacts with glass surfaces.
723215-1G
723215-5G
Dodecyl 2-bromoisobuty-
rate
O
O
Br
H3C
CH3
CH2(CH2)10CH3
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of dodecyl functionalized
telechelic polymers.
723223-1G
723223-5G
Octadecyl 2-bromoisobu-
tyrate
O
O
Br
H3C
CH3
CH2(CH2)16CH3
Atom Transfer Radical Polymerization (ATRP)
initiator for the creation of stearyl functionalized
telechelic polymers.
723231-1G
723231-5G
Metal Catalysts for ATRP
Name Formula Purity Cat. No.
Copper(I) chloride CuCl 99.995% trace metals basis 229628-10G
229628-100G
Copper(II) chloride CuCl
2
99.999% trace metals basis 203149-10G
203149-50G
Copper(I) bromide CuBr 99.999% trace metals basis 254185-10G
254185-100G
Copper(II) bromide CuBr
2
99.999% trace metals basis 437867-5G
437867-25G
Copper(I) iodide CuI 99.999% trace metals basis 215554-5G
215554-25G
215554-100G
21
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
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Acrylate Monomers
For a complete list of available acrylate monomers,
please visit sigma-aldrich.com/acrylic
H
2
C
OR
O
Monofunctional Acrylate Monomers
Name R Group Purity Additive Cat. No.
Sodium acrylate
Na *
97% - 408220-25G
408220-100G
Methyl acrylate
CH3 *
99% monomethyl ether hydroquinone
100 ppm as inhibitor
M27301-5ML
M27301-250ML
M27301-1L
M27301-2L
M27301-18L
Ethyl acrylate
CH3 *
99% hydroquinone monomethyl ether
15-20 ppm as inhibitor
E9706-100ML
E9706-1L
E9706-2L
Butyl acrylate CH3
*
99% monomethyl ether hydroquinone
10-55 ppm as inhibitor
234923-100ML
234923-1L
234923-18L
Hexyl acrylate
CH2(CH2)4CH3 *
98% hydroquinone 100 ppm as inhibitor 408905-25ML
408905-100ML
Lauryl acrylate
* CH2(CH2)10CH3
90% monomethyl ether hydroquinone
60-100 ppm as inhibitor
447315-100ML
447315-500ML
Octadecyl acrylate
* CH2(CH2)16CH3
97% - 409693-250G
409693-1KG
tert-Butyl acrylate
CH3
CH3
CH3
*
98% monomethyl ether hydroquinone
10-20 ppm as inhibitor
327182-5ML
327182-100ML
327182-1L
Isobutyl acrylate CH3
CH3
*
99% monomethyl ether hydroquinone
10-20 ppm as stabilizer
436305-250ML
436305-1L
2-Ethylhexyl acrylate CH3
CH3
* 98% monomethyl ether hydroquinone
10 ppm as inhibitor
290815-25ML
290815-1L
290815-3L
290815-18L
Isooctyl acrylate
CH3
CH3
*
- monomethyl ether hydroquinone
75-125 ppm as inhibitor
437425-100ML
437425-500ML
3,5,5-Trimethylhexyl acryl-
ate
CH3
CH3
CH3
CH3
*
- monomethyl ether hydroquinone
15-20 ppm as inhibitor
424021-25ML
1H,1H,2H,2H-Perfluorodecyl
acrylate
*
CF2(CF2)6CF3
97% monomethyl ether hydroquinone
100 ppm as inhibitor
474487-5ML
474487-25ML
2-Hydroxyethyl acrylate OH
*
96% monomethyl ether hydroquinone
200-650 ppm as inhibitor
292818-250ML
292818-1L
292818-18L
Hydroxypropyl acrylate,
mixture of isomers
OH *
95% hydroquinone monomethyl ether
200-650 ppm as inhibitor
370932-1L
370932-18L
4-Hydroxybutyl acrylate OH
*
90% hydroquinone 300 ppm as inhibitor
monomethyl ether hydroquinone
50 ppm as inhibitor
275573-25G
2-Carboxyethyl acrylate
OH
O
*
- - 552348-50ML
552348-500ML
2-(Dimethylamino)ethyl
acrylate
N
CH3
CH3
*
98% monomethyl ether hydroquinone
1,000 ppm as inhibitor
330957-100ML
330957-500ML
Isobornyl acrylate
CH3 H3C
CH3
*
- MEHQ 200 ppm as inhibitor 392103-100ML
392103-500ML
392103-1L
Pentabromophenyl acrylate
Br
Br
Br
Br
Br
*
96% - 592552-5G
Pentabromobenzyl acrylate
Br
Br
Br
Br
Br
*
98% - 640263-1G
640263-5G
3-(Trimethoxysilyl)propyl
acrylate Si OCH
3
OCH
3
OCH
3
*
92% BHT 100 ppm as inhibitor 475149-5ML
475149-25ML
22
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Name R Group Purity Additive Cat. No.
Di(ethylene glycol) ethyl
ether acrylate
O
O CH3 *
90% monomethyl ether hydroquinone
1000 ppm as inhibitor
408298-5ML
408298-250ML
408298-1L
Di(ethylene glycol) 2-ethyl-
hexyl ether acrylate
O
O
CH3
CH3 *
- monomethyl ether hydroquinone
500 ppm as inhibitor
407542-100ML
Poly(ethylene glycol) meth-
yl ether acrylate
*
O
CH3
n
- BHT 300 ppm as inhibitor
MEHQ 100 ppm as inhibitor
454990-250ML
454990-1L
Poly(propylene glycol)
acrylate
O
O
CH3
H
*
n
- MEHQ 200-400 ppm as inhibitor 469815-100ML
469815-500ML
Polyfunctional Acrylate Monomers
Name R Group Additive Cat. No.
1,4-Butanediol diacrylate
O
O
CH2
*
hydroquinone ~75 ppm as inhibitor 411744-25ML
411744-100ML
1,6-Hexanediol diacrylate CH2(CH2)4CH2O
O
CH2
* monomethyl ether hydroquinone
100 ppm as inhibitor
246816-100G
246816-500G
Tri(propylene glycol) diacry-
late, mixture of isomers
O
CH3
O
CH3
O
CH3 O
CH2
*
monomethyl ether hydroquinone
250 ppm as inhibitor
246832-100G
246832-500G
Trimethylolpropane triacrylate
H3C
O
O
CH2
O
CH2
O
*
monomethyl ether hydroquinone
100 ppm as inhibitor
246808-5G
246808-100G
246808-500G
Pentaerythritol triacrylate
* O
CH2
O
OH O
H2C
O
monomethyl ether hydroquinone
300-400 ppm as inhibitor
246794-100G
246794-500G
Pentaerythritol tetraacrylate
O
O
O
O
CH2
CH2
O
H2C
O
*
monomethyl ether hydroquinone
350 ppm as inhibitor
408263-5ML
408263-100ML
408263-250ML
Dipentaerythritol penta-/hexa-
acrylate
O
OR' OR'
O
OR' OR'
OR'
*
R' = H or *
O
CH2
monomethyl ether hydroquinone
500 ppm as inhibitor
407283-100ML
407283-500ML
-Substituted Acrylate Monomers
Name Structure Purity Cat. No.
Methyl -bromoacrylate
H2C
Br
O
OCH3
98% 588466-1G
Methyl 2-(bromomethyl)acrylate
H2C
Br
OCH3
O 97% 302546-1G
302546-5G
tert-Butyl 2-bromoacrylate
H2C
O
Br
O CH3
CH3
CH3
95% 588458-1G
Ethyl 2-cyanoacrylate
H2C
O CH3
CN
O - E1505-5G
E1505-10G
Ethyl 2-(bromomethyl)acrylate
H2C
O CH3
O
Br
98% 425222-1G
425222-5G
Methyl 2-acetamidoacrylate
H
2
C
NH
OCH
3
O
CH
3
O
98% 317519-1G
317519-5G
23
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Acrylamide Monomers
For a complete list of available acrylamide and methacrylamide
monomers, please visit sigma-aldrich.com/acrylic
H
2
C
N
H
O
R
Name R Group Purity Additive Cat. No.
N,N-Dimethylacrylamide
CH
3
N
CH
3
O
H
2
C
99% monomethyl ether hydroquinone
500 ppm as stabilizer
274135-5ML
274135-100ML
274135-500ML
Acrylamide
H *
99% - A8887-100G
A8887-500G
A8887-1KG
A8887-2.5KG
N-Isopropylacrylamide
CH
3
CH
3
*
97% - 415324-10G
415324-50G
N-tert-Butylacrylamide
CH
3
CH
3
CH
3
*
97% - 411779-100G
N-(Hydroxymethyl)acrylamide
solution
OH
*
- monomethyl ether hydroquinone
30 ppm as inhibitor
245801-5G
245801-100G
245801-1KG
N-Hydroxyethyl acrylamide
OH
* 97% monomethyl ether hydroquinone
3,000 ppm as stabilizer
697931-100ML
N-[Tris(hydroxymethyl)methyl]
acrylamide
*
OH
HO OH
93% - 364959-5G
364959-25G
N-(Butoxymethyl)acrylamide
O CH
3
*
- hydroquinone monomethyl ether
100 ppm as inhibitor
461067-100ML
N-(Isobutoxymethyl)acrylamide
O
CH
3
CH
3
*
- monomethyl ether hydroquinone
200 ppm as inhibitor
436534-100ML
Diacetone acrylamide CH
3
H
3
C
CH
3
O
*
99% - 222348-5G
222348-100G
222348-500G
N,N-Ethylenebis(acrylamide)
N
H
O
CH
2 *
- - 358878-5G
N-Phenylacrylamide
*
99% - 530042-10G
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Asymmetric Polymerization in a Chiral Liquid
Crystal Reaction Field
Kazuo Akagi
Department of Polymer Chemistry, Kyoto University
Katsura, Kyoto 615-8510, Japan
Email: [email protected]
Introduction
It is well known that polyacetylene is a one-dimensional conjugated
macromolecule and a good representative for conducting polymers.
1
Pristine polyacetylene is a typical semiconductor, but its electrical
conductivity can be amplified by over 14 orders of magnitude through
doping.
2,3
The maximum conductivity reported to date is more than
10
5
S/cm,
4
which is comparable to those of copper and gold. It has been
generally accepted that polyacetylene has a planar structure, irrespective
of cis and trans forms, due to the strong -conjugation between the
sp
2
hybridized carbon atoms in the polymer chain. If it were possible to
modify such a planar structure of polyacetylene into a helical one,
5,6
one
might expect novel electromagnetic and optical properties.
7,8
Here,
we present a modern polymerization method for acetylene in an
asymmetric reaction field using a chiral nematic liquid crystal (N*-LC)
which is also called a cholesteric LC, which demonstrates the formation
of a polyacetylene film comprised of helical chains and fibrils.
6,9-14
Polymerization that results in helical geometry from primary to
higher-order spiral morphology is discussed.
Chiral Dopants and N*-LCs
The N*-LC to be used as an asymmetric solvent is prepared by adding a
small amount of chiral compound, which serves as a chiral dopant, into
a nematic LC (Figure 1). The formation of a N*-LC is recognized when
the Schlieren texture characteristic of the nematic LC changes into a
striated Schlieren or a fingerprint texture as seen under a polarized
optical microscope (POM). The distance between the striae corresponds
to half the helical pitch of the N*-LC. Note that as the degree of twisting
in the N*-LC increases, the observed helical pitch is reduced.
Chiral dopant
Nematic LC ( N-LC )
N-LC N*-LC
1
/
2

P
i
t
c
h
100 m 50 m
Chiral nematic LC ( N*-LC )
Figure 1. Chiral nematic LC (N*-LC) induced by an addition of chiral dopant into nematic
LC. Schlieren texture (left) and fingerprint texture (right) are observed for nematic and
chiral nematic LCs, respectively, in polarized optical microscope.
The helical pitch of the N*-LC can be adjusted by two methods:
changing the concentration or changing the twisting ability of the chiral
dopant. It should be noted however that changing the concentration of
the chiral dopant affects the mesophase temperature region of the
N*-LC. Namely, it becomes narrower as the dopant concentration
increases, eventually resulting in destruction of the mesophase when
the concentration reaches a critical value. As a result, the alternative
approach of using a chiral compound with greater twisting ability is
employed. Axially chiral binaphthyl derivatives are good candidates
for chiral dopants,
15
since they have been reported to possess
larger twisting abilities than asymmetric carbon containing chiral
compounds.
16
(R)- & (S)-1,1-bi-naphthyl-2,2-di-[para-(trans-4-n-pentyl-
cyclohexyl)phenoxy-1-hexyl]ether were synthesized through Williamson
etherification reactions of optically pure (R)-(+)- and (S)-(-)-1,1-bi-2-
naphthols respectively which have been functionalized with phenyl-
cyclohexyl derivatives. These materials will be referred to as (R)- and
(S)-PCH506-Binol (Figure 2). The substituent is composed of a phenyl-
cyclohexyl (PCH) moiety, an n-pentyl group (5 carbon chain), and a
hexamethylene chain linked with an ether-type oxygen atom,
[-(CH
2
)
6
O- , 06], and thus abbreviated as PCH506.
N-LC N*-LC
C
3
H
7
O(CH
2
)
6
O C
5
H
11
C
5
H
11
O(CH
2
)
6
O
OC
2
H
5
C
3
H
7
PCH302
PCH304
OC
4
H
9
Catalyst
Chiral dopants Nematic LCs
Ti(O-n-Bu)
4
Et
3
AI
(R)-, (S)-PCH506-Binol
Figure 2. Construction of asymmetric reaction field for acetylene polymerization by
dissolving Ziegler-Natta catalyst, Ti(O-n-Bu)
4
AlEt
3
, into the chiral nematic LC. The
N*-LC includes an axially chiral binaphthyl derivative, (R)- or (S)- 2,2-PCH506-Binol.
To prepare an induced chiral nematic LC, 5-14 weight % of (R)- or
(S)-PCH506-Binol was added as a chiral dopant to an equimolar mixture
of the nematic LCs 4-(trans-4-n-propylcyclohexyl)ethoxybenzene
(PCH302) and 4-(trans-4-n-propylcyclohexyl) butoxybenzene (PCH304).
The PCH506 substituent group in the (R)- and (S)-PCH506-Binol
enhances the miscibility between the nematic LC mixture and the
binaphthyl derivative used as the chiral dopant. Usage of a similar
substituent with a shorter methylene spacer such as PCH503 or normal
alkyl substituent gave insufficient miscibility, yielding no chiral nematic
phase. In polarizing optical micrographs of the mixture of PCH302,
PCH304, and (R)-PCH506-Binol (abbreviated as R-1) and that of PCH302,
PCH304, and (S)-PCH506-Binol (abbreviated as S-1), a striated Schlieren
or a fingerprint-type texture, characteristic of chiral nematic LC phases, is
observed (Figure 1).
25
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Acetylene Polymerization in N*-LC
At first it should be noted that although each component (PCH302 or
PCH304) shows a LC phase, the LC temperature region is very narrow,
i.e., less than 1 to 2 C. This would be unsuitable for acetylene
polymerization in a nematic LC or N*-LC reaction field, because the
exothermal heat evolved during the acetylene polymerization would
raise the temperature inside the reaction flask, and destroy the LC phase
creating an isotropic one. Hence, an appropriate LC mixture is prepared
by mixing the two LC components in equal amounts. In the LC mixture,
the nematic-isotropic temperature, T
N-I
, is raised while the crystalline-
nematic temperature, TC-N, is lowered. In fact, the mixture exhibited the
LC phase in the 20 to 35 C region. Subsequently, the change of TN-I
upon an addition of Ti(O-n-Bu)
4
- AlEt
3
catalyst was examined through
DSC measurement. Even after taking into account the effect of
supercooling for LCs, the catalyst solution consisting of the LC mixture
and the chiral dopant had an available temperature range for
polymerization from 5 to 25 C. This sufficiently wide temperature region
enabled us to perform the acetylene polymerization in the N*-LC phase.
The Ziegler-Natta catalyst consisting of Ti(O-n-Bu)4 and Et3Al was
prepared using the (R)- or (S)-chiral nematic LC as a solvent (Figure 2).
The concentration of Ti(O-n-Bu)
4
was 15 mmol/L, and the mole ratio of
the cocatalyst to catalyst, [Et
3
Al] / [Ti(O-n-Bu)
4
], was 4.0. The catalyst
solution was aged for 30 min at room temperature. During the aging,
the N*-LC containing the catalyst showed no noticeable change in
optical texture, and only a slight lowering of the transition temperature
by 2 to 5 C. The transition temperature between the solid and chiral
nematic phases was 16 to 17 C, and that between the chiral nematic
and isotropic phases was 30 to 31 C. No solidification was observed
down to -7 C as a result of supercooling. Thus the (R)- and (S)-chiral
nematic LCs are confirmed to be chemically stable in the presence
of the catalyst. It is therefore suitable to employ these LCs as an
asymmetric solvent for acetylene polymerization. Acetylene gas
(99.9999 % purity) was used without further purification. The polymer-
ization temperature was kept between 17 to 18 C to maintain the chiral
nematic phase, by circulating cooled ethanol through an outer flask
covering the flask. The initial acetylene pressure was 11.6 to 22.6 Torr
and the polymerization time was between 10 to 43 minutes. After
polymerization, the polyacetylene films were carefully removed from the
container and washed with toluene several times under argon gas at
room temperature. The films were dried under vacuum on a PTFE sheet
and stored in a freezer at -20 C.
Characterization of Helical
Polyacetylene Film
Scanning electron microscope (SEM) images of the polyacetylene films
show that multiple domains of spiral morphology are formed (Figure 3),
and each domain is composed of a helical structure of fibrils with one-
handed twist direction (Figure 3 inset). The multi-domain type fibril
morphology of polyacetylene seems to replicate that of the N*-LC used
in the interfacial acetylene polymerization.
Figure 3. Hierarchical spiral morphology of helical polyacetylene film. The figure and
inset show scanning electron microscope (SEM) photographs of multi domain type spiral
morphology and right-handed screwed bundles of fibrils in a domain, respectively.
Closer observation of SEM images indicates that helical polyacetylenes
synthesized in the (R)- and (S)-chiral N*-LCs form the twisted bundles of
fibrils and even screw-shaped fibrils with counterclockwise and
clockwise directions, respectively. This result implies that the twist
direction of helical polyacetylene is controllable by choosing the helicity,
i.e., chirality of the dopant, when the N*-LC induced by the chiral dopant
is employed as an asymmetric polymerization solvent. The helical pitch
of the N*-LC depends on the helical twisting ability of the chiral dopant,
as well as its concentration and optical purity. This means that the
helical pitch of the polyacetylene chain can be also varied by changing
helical twisting ability of the chiral dopant. Another axially chiral dopant,
(R)- or (S)-6,6-PCH506-2,2-Et-Binol
14,15
gave a shorter helical pitch of
N*-LC by 0.3 m than the corresponding (R) or (S)-PCH506-Binol.
Acetylene polymerization using these types of highly twisted N*-LCs,
designated (R-2)- and (S-2)-chiral nematic LCs, afforded clearer spiral
morphologies consisting of helical bundles of fibrils (Figure 4). Namely,
these bundles are aligned parallel to each other in the microscopic
regime, and forms spiral morphologies in the macroscopic regime. It is
noteworthy that the higher order structures observed in Figure 3
resemble the helical self-assembled microstructure of biological
molecules such as lipids, which are rarely formed in synthetic polymers.
This validates the use of N*-LC as a template polymerization medium for
controlling a higher order structure of synthetic polymer.
4 m
(R) (S)
C
5
H
11
(CH
2
)
6
OEt
O
C
5
H
11
(CH
2
)
6 O
OEt
C
5
H
11
(CH
2
)
6
OEt
O
C
5
H
11
(CH
2
)
6 O
OEt
4 m
Figure 4. SEM photographs of helical polyacetylene films synthesized in the N*-LCs
including (R)- 6,6-PCH506-2,2-Et-Binol. The left- and right-handed screw directions of
helical polyacetylenes are determined by the chirality of the chiral dopants with R- and
S-configurations, respectively.
26
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The bundles of fibrils for helical polyacetylenes synthesized in the
(R-2)- and (S-2)-N*-LCs are twisted counterclockwise and clockwise,
respectively (Figure 4). The hardness of helical polyacetylene are
opposite to those of the corresponding (R-2)- and (S-2)-N*-LC whose
directions are confirmed to be clockwise and counterclockwise,
respectively, through the miscibility test with cholesteryl oleyl carbonate
(Aldrich Prod. No. 151157). This is the same situation as the case of the
(R-1)- and (S-1)-N*-LCs including (R)- and (S)-PCH506-Binol. In circular
dichroism (CD) spectra of the polyacetylene thin films synthesized under
the (R-2)- and (S-2)-chiral nematic LCs, positive and negative Cotton
effects are observed respectively in the region from 450 to 800 nm
corresponding to -> * transition of polyacetylene chain, despite the
absence of chiroptical substituent in side chains. This indicates that the
polyacetylene chain itself is helically twisted. It is evident that the above
Cotton effect is not due to the chiral dopant [(R)- or (S)- 6,6-PCH506-2,2-
Et-Binol], because the Cotton effect of the chiral dopant is only observed
at shorter wavelengths such as 240 ~ 340 nm. From these results, it can
be concluded that left-handed (counterclockwise) and right-handed
(clockwise) helical polyacetylene chains are formed in (R)- and (S)-chiral
nematic LCs, respectively, and that these helical chains are bundled
through van der Waals interactions to form helical fibrils with the
opposite helical directions to those of the N*-LCs. The bundles of
fibrils further form the spiral morphology with various sizes of
domains (Figure 5).
Primary
Structure
Planar
chain
Helical
chain
Fibril Bundle
of
Fibrils
Higher Order
Structure
Spiral
form
SEM
photograph
Spiral
morphology
SEM
photograph
2 m
15 m
Figure 5. Super-hierarchical helical structures from primary to higher order in
helical polyacetylene.
The present helical polyacetylene films have high trans content of
90%, and become highly conductive upon iodine doping. In fact, the
electrical conductivities of the doped films are 1.5 ~ 1.8 10
3
S/cm at
room temperature, which are comparable to those of metalic materials.
The iodine-doped polyacetylene showed the same Cotton effect as that
of non-doped polyacetylene, although the CD peak was slightly shifted
to shorter wavelengths. This indicates that the helical structure is
preserved even after iodine doping. Furthermore, CD and X-ray
diffraction measurements showed that the helical structure was also
preserved after heating up to 150 C (which corresponds to the
isomerization temperature from cis to trans form). It is well-known that
the most stable structure of polyacetylene is the planar one. However,
since the polyacetylene is actually insoluble and infusible, the helical
structure formed during the polymerization can be preserved even if it is
washed by toluene (Aldrich Prod. No. 244511) or thermally heated
below the isomerization temperature. In other words, the insolubility
and infusibility characteristics of polyacetylene are important for
preserving the meta-stable helical structure.
17
Lastly, it is worth noting
that the present polymerization method using the N*-LC (i.e., cholesteric
LC) as an asymmetric reaction field has profound versatility for the
synthesis of helical -conjugated polymers that do not contain chiral
substituents in side chains. In fact, very recently, a number of helical
conjugated polymers such as polybithiophene, polyethylenedioxythio-
phene derivatives, and phenylene-thiophene copolymers were
synthesized through chemical and/or electrochemical polymerizations
in N*-LCs environments.
18-20
Conclusion
We present current progress in the synthesis and also the novel
properties of conjugated polymers by focusing on helical polyacetylene
with super-hierarchical structure.
14
Interfacial polymerization of acety-
lene was carried out in asymmetric reaction field consisting of a N*-LC
and a Ziegler-Natta catalyst. Since the N*-LC is composed of a nematic
LC and a chiral compound such as axially chiral binaphthyl derivative
with R- or S-configuration, the helical directions of polyacetylene chain
and fibril bundles and even the spiral morphology are determined by
the chirality of the chiral dopant. The helical directions of the fibril and
the bundle of the fibril in helical polyacetylene were found to be
opposite to that of the N*-LC. The hierarchical spiral morphology
involving the primary and higher order structures is generated in a
synthetic polymer such as polyacetylene by using N*-LC as an
asymmetric polymerization solvent.
References
(1) Chien, J. C. W., Polyacetylene - Chemistry, Physics and Material Science Academic
Press, Orlando, FL, 1984.
(2) Shirakawa, H., Louis, E., MacDiarmid, A. G., Chiang, C. K., Heeger, A. J., J. Chem. Soc.
Chem. Commun. 1977, 578.
(3) Chiang, C. K., Fincher, C. R., Park, Y. W., Heeger, A. J., Shirakawa, H., Louis, E. J.,
Gau, S. C., MacDiarmid, A. G., Phys. Rev. Lett. 1977, 39, 1098.
(4) Naarrmann, H., Theophilou, N., Synth. Met. 1987, 22, 1.
(5) Bozovic, I., Mod. Phys. Lett. B 1987, 1, 81.
(6) Akagi, K., Piao, G., Kaneko, S., Sakamaki, K., Shirakawa, H., Kyotani, M., Science 1998,
282, 1683.
(7) Aleshin, A. N., Lee, H. J., Park, Y. W., Akagi, K., Phys. Rev. Lett. 2004, 93, 196601.
(8) Oh-e, M., Yokoyama, H., Yorozuya, S., Akagi, K., Belkin, M. A., Shen, Y. R., Phys. Rev. Lett.
2004, 93, 267402.
(9) Akagi, K., Guo, S., Mori, T., Goh, M., Piao, G., Kyotani, M., J. Am. Chem. Soc. 2005,
127, 14647.
(10) Goh, M., Kyotani, M., Akagi, K., J. Am. Chem. Soc. 2007, 129, 8519.
(11) Goh, M., Matsushita, T., Kyotani, M., Akagi, K., Macromolecules 2007, 40, 4762.
(12) Mori, T., Kyotani, M., Akagi, K., Macromolecules 2008, 41, 607.
(13) Mori, T., Sato, T., Kyotani, M., Akagi, K., Macromolecules 2009, 42, 1817.
(14) Akagi, K., Chem. Rev. 2009, 109, 5354.
(15) Goh, M., Akagi, K., Liq. Cryst. 2008, 35, 953.
(16) Akagi, K., Higuchi, I., Piao, G., Shirakawa, H., Kyotani, M., Mol. Cryst. Liq. Cryst.
1999, 332 463.
(17) Kyotani, M., Matsushita, S., Nagai, T., Matsui Y., Shimomura M., Kaito, A.,
Akagi, K., J. Am. Chem. Soc. 2008, 130, 10880.
(18) Goto, H., Akagi, K., Macromol. Rapid Commun. 2004, 25, 1482.
(19) Goto, H., Akagi, K., Macromolecules 2005, 38, 1091.
(20) Goto, H., Akagi, K., Angew. Chem. Int. Ed. 2005, 44, 4322.
27
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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Thiophene and Pyrrole Monomers
Thiophene and pyrrole monomers are easily polymerized electrochemically or using simple chemical polymerization methods to form electroactive
polymers. These polymerizations can be carried out in liquid crystal templates, similar to the methodology described in the article by Professor Akagi.
Here we list a selection of thiophene and pyrrole monomers.
For a complete list of available thiophene and pyrrole monomers and other synthetic tools, please visit sigma-aldrich.com/synthetic
Name Structure Purity Cat. No.
Thiophene
S
99% T31801-5G
T31801-100G
T31801-500G
3,4-Dimethoxythiophene
S
OCH3 H3CO 97% 668257-5G
3,4-Ethylenedioxythiophene
S
O O
- 483028-10G
Hydroxymethyl EDOT
S
O O
HO 97% 687553-500MG
3,4-Propylenedioxythiophene
S
O O
97% 660485-100MG
660485-500MG
3,4-(2,2-Dimethylpropylenedioxy)thiophene
S
O O
CH3 H3C 97% 660523-500MG
3,4-(2,2-Diethylpropylene)dioxythiophene
O O
S
H3C CH3 97% 669210-250MG
3-Methylthiophene
S
CH3
98.0%, GC 69370
3-Thiopheneethanol
S
OH 99% 228796-5G
228796-25G
3-Butylthiophene
S
CH3
96% 510424-1G
510424-5G
3-Hexylthiophene
S
CH2(CH2)4CH3
99% 399051-1G
399051-5G
3-Octylthiophene
S
CH2(CH2)6CH3
97% 424285-1G
424285-5G
3-Decylthiophene
S
CH2(CH2)8CH3
97% 456357-5G
3-Dodecylthiophene
S
CH2(CH2)10CH3
97% 456365-1G
456365-5G
3-Phenylthiophene
S
95% 399043-1G
2,2-Bithiophene
S S
97% 241636-10G
2,2:5,2-Terthiophene
S
S
S
99% 311073-1G
28
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit sigma-aldrich.com/matsci. sigma-aldrich.com
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Name Structure Purity Cat. No.
Pyrrole
N
H
98% 131709-25ML
131709-100ML
131709-500ML
3,4-Ethylenedioxypyrrole
N
H
O O
- 648310-2ML
648310-10ML
3,4-Propylenedioxypyrrole
N
H
O O
- 648329-2ML
648329-10ML
Methyl 1H-pyrrole-3-carboxylate
N
H
OCH3
O 97% 685399-250MG
685399-1G
4-(3-Pyrrolyl)butyric acid
N
H
OH
O
95% 682578-100MG
682578-500MG
N-Methylpyrrole
N
CH3
99% M78801-100ML
1-(Dimethylamino)pyrrole
N
N
H3C CH3
99% 247790-5G
1-(2-Cyanoethyl)pyrrole
N
CN
99% C91352-25G
1H-Pyrrole-1-propanoic acid
N O
OH
97% 687545-1G
11-(1H-pyrrol-1-yl)undecane-1-thiol
N
CH2(CH2)9CH2SH
96% 717223-1G
1-Phenylpyrrole
N
99% 131474-10G
N-Benzylpyrrole
N
97% 566322-5G
1-(4-Methylphenyl)-1H-pyrrole
N
CH3
97% 452963-5G
1-(4-Methoxyphenyl)-1H-pyrrole
N
O
H3C
97% 452955-1G
452955-5G
1-(2-Aminophenyl)pyrrole
N
NH2
98% 196940-1G
196940-10G
1-(4-Nitrophenyl)-1H-pyrrole
NO2
N
97% 447358-1G
447358-5G
29
For questions, product data, or new product suggestions, please contact Aldrich Materials Science at [email protected].
Materials Science
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