Controlled Radical Polymerization Guide

Controlled Radical
Polymerization Guide
ATRP | RAFT | NMP
Materials Science
Chain-growth polymerization has been successfully performed

for many decades through conventional free radical, anionic, or
cationic polymerization. These polymerization techniques generate
many important commodity polymers where their broad range
of molecular weight distribution gives rise to important physical
properties. While these techniques are useful for a number of
applications starting from a wide variety of monomers, several
applications benefit from using more precisely controlled polymers.
Living polymerization pioneered by Michael Szwarc enables
control over the polymer architecture, which includes molecular
weight, molecular weight distribution (polydispersity), functionality,
and composition. The occurrence of premature termination is
minimized, and molecular weight proceeds linearly with time
until all monomer is consumed or intentionally terminated. In the
1990s, new methods were developed which enabled an adaptation
of living ionic polymerization to living radical polymerization
(LRP), also referred to as controlled radical polymerization (CRP).
Controlled radical polymerization has branched into three
fundamental techniques which are listed below.
yyAtom Transfer Radical Polymerization (ATRP)

yyReversible Addition/Fragmentation Chain Transfer
Polymerization (RAFT)
yyNitroxide-mediated Polymerization (NMP)
CRP can be utilized with a broad range of vinyl monomers for a
wide variety of applications. Moreover, CRP enables a new level
of materials design and is accessible to all levels of synthetic
expertise due to the robustness of the polymerization conditions.
Figure 1 illustrates the trend in literature citations for the main
CRP techniques.
1200
Table 1. Benefits and limitations of ATRP, RAFT, and NMP processes.
Primary
Benefits
ATRP
RAFT
NMP
yyVersatile
yyVersatile
yyNo use of transition

metals
yyAbility to tailor catalyst yyNo use of transition

to meet specific needs
metals
yyHigh potential for odor yyLeast versatile

and discoloration
yyMany variables affecting (especially for low
molecular weights)
polymer characteristics
Polymers generated by controlled radical polymerization are used

in many applications. Surface modification, commonly performed
through ATRP, enables advancement in many applications which
rely on tailored hydrophilicity, adhesive properties, or nanoparticle
functionalization. Block copolymers for bio-applications, commonly
performed through RAFT or ATRP, enable advancements in drug
delivery, bio-mineralization, bio-compatibilization, and hydrogel
applications. Block copolymers generated from NMP are used in
pigment dispersion, memory devices, composite manufacturing,
and many others.
This guide provides a fundamental review of ATRP, RAFT, and
NMP techniques, as well as corresponding procedures and
product information to utilize these techniques. The guide has
been arranged in four sections: the ATRP section contains four
articles, two procedures and tables for initiators and catalysts; the
RAFT section contains three articles, two procedures and RAFT
agent tables; the NMP section contains an article and an NMP
agent product table; and the monomer section contains tables
of six monomer classes. We hope that this publication will enable
chemists and engineers to explore different
CRP techniques.
Sebastian Grajales, Ph.D.
Aldrich Materials Science
Milwaukee, WI 53209
RAFT
NMP
800
600
400
200
2011
2010
2009
2008
2007
2006
2005
2004
2003
2002
2001
2000
1999
1998
1997
1996
1995
1994
Year
Figure 1. SciFinder search results as of 2011 for ATRP, RAFT, and NMP technologies.
All of these technologies are popular in the research community

and are being explored for industrial adoption. ATRP has
consistently held the most citations. RAFT technology has gained
a substantial increase in publications over the last 5-8 years. NMP
remains relevant in research with approximately 150 annual
citations since 2005. Table 1 is a brief summary of benefits and
limitations of the different CRP techniques.
Aldrich.com
yyLow potential for odor

and discoloration
Primary
yyUse of transition
Limitations
metals
ATRP
1000
Citation Count
Preface
Preface
TO ORDER: Contact your local Sigma-Aldrich office (see back cover), or visit Aldrich.com/matsci.
#2757 CRP, TOC, edited 0228
TOC
Nitroxide-mediated Polymerization (NMP)................31
ATRP for Everyone: Ligands and Initiators for the

Clean Synthesis of Functional Polymers............................................... 2
Block Copolymer Synthesis Using a Commercially

Available Nitroxide-mediated Radical
Polymerization (NMP) Initiator .................................................................. 31
Authors: Jakubowski, Tsarevsky, McCarthy, and

Matyjaszewsky
Tools for Performing ATRP.............................................................................. 6
Authors: Lee, Wooley
NMP Initiators......................................................................................................... 34
Authors: Grajales
Copper(I)-mediated Living Radical Polymerization in

the Presence of Pyridylmethanimine Ligands ................................. 9
Authors: Haddleton
Typical Procedures for Polymerizing via ATRP ............................. 11

Authors: Haddleton
Applying ARGET ATRP to the Growth of Polymer

Brush Thin Films by Surface-initiated Polymerization............. 12
Authors: Zhu, Edmondson
ARGET ATRP: Procedure for PMMA Polymer

Brush Growth ......................................................................................................... 15
Monomer Index ......................................................................35
Table of Contents
Atom Transfer Radical Polymerization (ATRP) ........... 2
Styrene Monomers............................................................................................. 35
Acrylate Monomers............................................................................................ 38
Acrylamide Monomers.................................................................................... 41
Methacrylate Monomers................................................................................ 42
Methacrylamide Monomers ........................................................................ 45
Vinyl Amide and Vinyl Ester Monomers............................................ 46
Authors: Zhu, Edmondson
ATRP Initiators........................................................................................................ 16
Ligands for ATRP Catalysts........................................................................... 17
Metal Salts for ATRP Catalysts ................................................................... 18
Reversible Addition/Fragmentation Chain

Transfer Polymerization (RAFT) ....................................... 19
A Micro Review of Reversible Addition/Fragmentation
Chain Transfer (RAFT) Polymerization.................................................. 19
Authors: Moad, Rizzardo, Thang
Concepts and Tools for RAFT Polymerization............................... 22

Authors: CSIRO and Aldrich Researchers
Typical Procedures for Polymerizing via RAFT ............................. 23

Authors: CSIRO Researchers
Universal/Switchable RAFT Agents for Well-defined

Block Copolymers: Agent Selection
and Polymerization............................................................................................ 24
Authors: Aldrich Researchers
Polymerization Procedure with Universal/Switchable

RAFT Agents............................................................................................................ 25
Authors: CSIRO and Aldrich Researchers
RAFT Agents............................................................................................................ 27
Switchable RAFT Agents................................................................................ 29
Radical Initiators ................................................................................................... 30
For questions, product data, or new product suggestions, contact Aldrich Materials Science at [email protected].
ATRP for Everyone: Ligands and Initiators

for the Clean Synthesis of Functional Polymers
ATRP
ATRP for Everyone: Ligands and Initiators for the Clean Synthesis
of Functional Polymers
Catalysts for ATRP
Wojciech Jakubowski, Nicolay V. Tsarevsky, Patrick McCarthy*, Krzysztof Matyjaszewski

ATRP Solutions, Inc., 166 N. 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.
k
k
R(
X)n + Mt /L
Z
act
+ X MtZ+1/L
R
k
t
deact
(R
R
H+ R
I-X
I
or
+ X MtZ+1/L
(
Ox
Red
AIBN
ICAR ATRP
variable
materials
ARGET ATRP
library
R
[M]0 / [R(X)n]0
n
Scheme 1. Schematic illustration of the ATRP process (top) and an example of

a star-shaped polymer library.
ATRP is a 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 Mtz/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-Mtz+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 kp), with each other
(termination with the rate constant, kt) or with X-Mtz+1/L (deactivation
with the rate constant, kdeact). 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
Mtz/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
kact / 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 CuI and CuII) 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 (Me6TREN, 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
decreasing the 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)
ethylhexanoate8,9,11-13 (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
Me6TREN
TPMA
Aldrich Prod.
No. 723142
Aldrich Prod.
No. 723134
Figure 1. Ligands for Cu-mediated ATRP using ppm amounts of catalyst.
Aldrich.com
TO ORDER: Contact your local Sigma-Aldrich office (see back cover) or visit Aldrich.com/matsci.
ATRP
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, Aldrich Prod. No. 221775)
and TPMA (10.1 mg, 3.49 10-2 mmol, Aldrich Prod. No. 723134) to a
10 mL flask equipped with magnetic stirring bar.
Add DMF (4 mL, Aldrich Prod. No. D158550) to solubilize CuBr2/TPMA.
Stir for 10 min to obtain a homogeneous yellowish solution.
Add St (80.0 mL, 0.698 mmol, Aldrich Prod. No. 240869), AIBN (0.153 g,
0.0931 mmol, Aldrich Prod. No. 441090) and ethyl 2-bromoisobutyrate (0.68 mL, 4.65 mmol, Aldrich Prod. No. E14403) 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 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 %. Mn =
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 C to constant weight (ca. 24 h).

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 functionality11 and adjustable molecular
weight distribution.18 In addition, since the level of control in ARGET
and ICAR ATRP is only weakly affected by an excess of reducing
agent, the reactions 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/nm2), 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 Me6TREN 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 CuIIBr2/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
*Note: Time of the reaction may vary depending on a type of used

equipment and purity of chemical reagents.
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 of 100. As shown in Figure 2, the
polymerization is well-controlled: the linear first order kinetic plot of
Polymerization conditions for ICAR ATRP of styrene:

[St]0 / [EtBiB]0 / [CuBr2]0 / [TPMA]0 / [AIBN]0 100 / 1 / 0.005 / 0.005 / 0.2
T = 70 C ; DMF as internal standard (5 vol% versus St)
1.0x104
Ln([M]0/[M])
1.6
1.2
0.8
0.4
0.0
0
400
800
1200
103
2.0
8.0x103
1.8
6.0x103
1.6
4.0x103
1.4
2.0x103
1.2
0.0
0.0
Time [min]
Time [min]
t=1.3 h
t=2.5 h
t=5.0 h
t=10.0 h
t=21.0 h
102
PDI
Molecular weight [g/mol]
2.0
0.2
0.4
0.6
0.8
1.0
1.0
Conversion of St
104
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
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 / CUII / AIBN
(60 C, in anisole, (50 vol % vs. St))
Ligand
0.01
200/1/0.01/0.1
Me6TREN
(Aldrich Prod. No. 723142)
Cu
(ppm)
Time
(min)
Conv.
(%)
Mn
(theor.)
Mn
(SEC)
PDI
50
2760
44
8700
7900
1.12
50
2880
39
7800
6800
1.09
50
2880
29
5600
4500
1.62
50
2940
36
7200
5600
1.68
N
N
0.01
200/1/0.01/0.1
TPMA
N
N
N
N
200/1/0.01/0.1
PMDETA
200/1/0.01/0.1
dNbpy
0.01
N
0.02
C 9H 19
C 9H 19
Me6TREN 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 solution, to generate a variety of nanoscale structures.
The structures range from simple micellar or lamellar to complex gyroid.
Recent studies on block copolymer self assembly demonstrated that
nanoscale 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
PSt
PSt-b-PtBA
103
Mn
[g/mol]
PDI
DPIPBA
6,800
1.16
12
11,800
1.14
47
30,200
1.12
180
Mn=5,200 g/mol
PDI=1.11
DPPSt=50
GPC signal

ATRP
101
105
Figure 3. GPC traces and properties of PSt-b-PtBA block copolymer library.
Aldrich.com
ATRP
O
Initiators for ATRP

ATRP uses simple initiators, mainly alkyl halides R-X (X = Cl, Br).
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:
HO
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).
Hydroxy initiator
Aldrich Prod. No. 723150
Biodegradable (disulfide) initiator

Br
Br
O
11
Allyl initiator
Br
Br
Mn = ([M]0 / [RX]0) Conv MW(M)
Dodecyl initiator
Br
O
17
Stearyl initiator
Figure 5. Examples of ATRP initiators that can be used to prepare end-functionalized and
disulfide containing polymers.
Monomer M: styrene, acrylate,

methacrylate type
Br
FG
Br
O
Br
Br
O
O
FG: hydroxyl group

- modification of chain-end by reaction
of small molecules with OH group
- ring opening polymerization using OH
group as initiating site
O
O
O

1,25,26
Br
Br: bromine group

- extension with second
type of monomer
using ATRP
Br
Br
Difunctional initiator
Trifunctional initiator
Br
Br
Br
O
O
Br
Br
O
Tetrafunctional initiator
Br
O
O
Br
Br
O
O
Br
Br
Br
Br
Hexafunctional initiator
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-polymerization 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 endfunctionalized 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 containing a
functional group able to react with gold surfaces, and also gives the
polymers the ability to degrade in reducing environments.
Br: bromine group

- extension with
second type of
monomer using
ATRP
FG: disulfide group

- degradation of
polymer upon
reducing
environment
Br: bromine group

- extension with
second type of
monomer using
ATRP
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 architectures 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 endfunctional polymers accessible through ATRP.25

ATRP
Summary
Tools for Performing ATRP
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.
Sebastian Grajales, Ph.D.

Aldrich Materials Science
6000 N. Teutonia Ave. Milwaukee, WI 53209
Email: [email protected]
References
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(1)
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(3)
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Fischer, H. Macromolecules 1997, 30, 5666.
Dong, H.; Tang, W.; Matyjaszewski, K. Macromolecules 2007, 40, 2974.
Listak, J.; Jakubowski, W.; Mueller, L.; Plichta, A.; Matyjaszewski, K.; Bockstaller, M. R.
Macromolecules 2008, 41, 5919.
www.atrpsolutions.com
Chan, N.; Cunningham, M. F.; Hutchinson, R. A. Macromol. Chem. Phys. 2008, 209,
1797.
Dong, H.; Matyjaszewski, K. Macromolecules 2008, 41, 6868.
Pietrasik, J.; Dong, H.; Matyjaszewski, K. Macromolecules 2006, 39, 3914.
Hadjichristidis, N.; Pispas, S.; Floudas, G., Block Copolymers: Synthetic Strategies,
Physical Properties, and Applications. John Wiley & Sons, Inc.: Hoboken, 2003.
Hamley, I. W., Development in Block Copolymer Science and Technology. John Wiley &
Sons, 2004.
Coessens, V.; Pintauer, T.; Matyjaszewski, K. Prog. Polym. Sci. 2001, 26, 337.
Ouchi, M.; Terashima, T.; Sawamoto, M. Chem. Rev. 2009, 109, 4963.
Matyjaszewski, K.; Gnanou, Y.; Leibler, L., Macromolecular Engineering. Precise
Synthesis, Materials Properties, Applications. Wiley-VCH: Weinheim, 2007.
Controlled radical polymerization (CRP) techniques have been reviewed

in a number of articles1,2 and books,3 and include nitroxide-mediated
polymerization (NMP),4-7 reversible addition fragmentation chain transfer
(RAFT),8-10 and atom transfer radical polymerization (ATRP).11 All of these
CRP techniques operate by rapidly establishing an equilibrium between
a small fraction of active polymerizing chains and a majority of dormant
moieties. ATRP has proven to be versatile and effective in providing a
controlled polymerization environment for a wide range of vinyl
monomers including styrenes, (meth)acrylates, acrylonitriles, and
dienes.3 ATRP differs from conventional radical polymerization because
of the ability of a metal complex to dictate the rate of monomer
addition to the propagating polymer chain end. While the procedure to
perform normal ATRP is simple with essentially three components
(initiator, catalyst, and monomer) added to solvent, the equilibrium
equation describing the reaction is more complex, and is shown
in Figure 1.
Polymerization
Dormant
/
R -X + Cu 1+/L
(1)
(2)
k act
k deact
X --Cu 2+//L +
(3)
kp
(4)
+R
+M
(5)
kt
RR
(6)
Undesired Termination
Figure 1. The ATRP equilibrium equation, which resides predominantly to the left/
dormant side, includes dormant initiator R-X (1), catalyst composed of a transition metal
Cu with ligand L (2), oxidized catalyst (3), active radical or active initiator R (4), and
monomer M (5) and terminated polymer RR (6). The reaction rates are labeled with kx.
This equation may appear to have a high degree of complexity, but its
meaning and importance can be illustrated by three situations: a
polymer sitting dormant on the left side of the equilibrium; a polymer
reacting with monomer on the right side of the equilibrium (and
growing in molecular weight); and two radical end-groups combining to
terminate and kill the reaction (this is neither reversible nor desired). In
ATRP, the reaction resides on the left side of the equation most of the
time. This minimizes the likelihood for two radicals to exist near each
other at the same time and therefore minimizes termination. This control
over termination is the primary benefit of choosing ATRP. Another
important feature of ATRP is that only one radical is formed upon
activation. This is particularly important if surface-initiated polymerization
is desired because this minimizes solution polymerization.
The rate of reaction is marked by rate constants (kx) where the rate of
activation is kact, the rate of deactivation is kdeact, the rate of monomer
addition is kp, and the rate of termination is kt. The control over this
equilibrium highly depends on the choice of catalyst.
Aldrich.com
ATRP
Variations of ATRP
The catalyst (complex 2 in Figure 1) is a transition metal ion with

coordinated ligands, and complex 3 is the oxidized form of the complex.
(The difference between the two is that the oxidized complex 3 has the
halogen from the initiator and a charge of one higher than complex 2.)
A wide variety of transition metals have been reported to work with
ATRP, including Ti,12 Fe,13-17 Co,18 Ni,19-21 Mo,22-24 Ru,25-27 Rh,28 Pd,29
Re,30 Os,31 but the use of Cu dominates the literature. To simplify the
discussion, the rest of this article will refer to Cu.
Returning to Figure 1, the components that are added to the

polymerization solution for normal ATRP are initiator 1, catalyst 2, and
monomer 5. Catalyst 2 is oxygen-sensitive, so in an effort to minimize
handling of this compound, several variations of ATRP have been
developed. Newer variations of ATRP were developed primarily to
generate the air-sensitive catalyst 2 at the start of the reaction rather than
requiring it to be handled and added.
The catalyst complex 2 abstracts the halogen from the initiator (or chain
end) to activate the polymerization, so it has an important influence on
the reaction rates of the equilibrium. The ligand choice will have a
profound effect on kact and kdeact, which will cause a difference in the
rate of polymerization. Several ligands are shown plotted along the ratio
of (kact/kdeact) in Figure 2.
Speed
H 3C
N
N C 4H 9
10 -10
10 -9
10 -8
dBbpy
515477
10 -7
10 -6
Typical Reactants Added

N
Me6TREN
723142
10 -5
10 -4
N C 12H 25
Dodecyl-PMI
754412
PMDETA
369497
HMTETA
366404
(C H 2 ) 8 C H 3
N
dNbpy
482250
Me4cyclam
282804
N C 18 H 37
Octadecyl-PMI
754420 H C (H C )
2 8
3
Copper(II)
Catalyst
Concentration
(ppm)
ATRP
10,000
ICAR
Popular
Ligands
Reducing
Agent
Free
Radical
Initiator
0-variable
all nitrogen
containing
ligands
10
Me6TREN
and TPMA
AIBN
AGET
Me6TREN
and TPMA
tin(II)ethylhexanoate
ARGET
Me6TREN
and TPMA
tin(II)ethylhexanoate
10 -3
N
N
Polymerization
Copper(I)
Catalyst
Concentration
(ppm)
K ATRP = ( k act /k deact )

N
Detailing the competing reactions for all of these techniques is beyond

the scope of this article; however, the following table summarizes the
components added to perform the different ATRP reactions.
dMebpy
569593
bpy
D216305
Butyl-PMI
752606
10 -11
N
N
Initiators for Continuous Activator Regeneration (ICAR)

Activators Generated by Electron Transfer (AGET)
Activators ReGenerated by Electron Transfer (ARGET)
Reverse ATRP
Table 1. ATRP polymerization type and corresponding identity or concentration of

popular reactants added.
C H3
N C 8 H 17
Octyl-PMI
752592
ATRP: Choosing a Ligand for the Catalyst
TPMA
723134
Figure 2. Nitrogen-based ligands plotted against the ATRP equilibrium constant (KATRP)
with initiator EtBibb, in the presence of CuBr in MeCN at 22 C. Bidentate ligands are blue
diamonds, tridentate ligands are red triangles, and tetradentate are green squares.
Adapted from Tang, W. et al.32
This shows that, in general, the speed of the polymerization in terms of

the ligand structure is bidentate < tridentate < tetradentate. This can
also be thought of in terms of how much catalyst is needed to perform
the reaction. Less catalyst is needed with a large KATRP value.
Reverse ATRP
1,000
several
Simultaneous
reverse and
normal
1,000
several
AIBN
All of the newer ATRP variations eliminate the need to handle air
sensitive Cu1+. ICAR, AGET, and ARGET methods utilize substantially
lower concentrations of Cu catalyst over the other types. Table 2
summarizes the benefits and limitations of the various ATRP techniques:
Table 2. Benefits and limitations for ATRP techniques.
Polymerization
Benefit
Limitation
Normal ATRP
Versatile
High Cu content, unstable

catalyst precursor
ICAR
Low Cu content, catalyst

precursors more stable
AIBN might cause side reactions
AGET

High Sn content (FDA approved)
ARGET

High Sn content (FDA approved)
Reverse ATRP
Simple, catalyst
Limited end group functionality;

only linear; targeting MW difficult
Simultaneous reverse
and normal ATRP
Catalyst precursor more stable
AIBN might cause side reactions
The relatively high levels of residual Cu by traditional ATRP are

problematic for biomedical and food packaging applications where it is
required to minimize or eliminate toxins, such as heavy metals. Polymers
generated by traditional ATRP contain substantial residual Cu catalyst if
not properly purified. ICAR, AGET, and ARGET operate at low levels of Cu
during polymerization and therefore need minimal subsequent
purification for catalyst removal. These new versions of ATRP enable their
utility to prepare well-defined copolymers for these high value
applications.
(Fast)*
The appropriate ATRP technique can be chosen based on the needs of

the application. Figure 2 can be used to select a ligand based on catalyst
activity; however, the effect of the ligand on the resulting molecular
weight distribution is not illustrated. The plot of the KATRP vs. kdeact is
shown in Figure 3 and illustrates catalyst activity as a function of control
over the polymerization.32 Wei Tang and co-workers developed this plot
which shows the PDI better correlates to the rate of deactivation kdeact
rather than the value of KATRP found in Figure 2.32
Less Cu Required
ATRP
References
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
Me4Cyclam
282804
Me6TREN
723142
(9)
(10)
(11)
(12)
TPMA
723134
Activity
(Speed)*
(13)
dNbpy
482250
HMTETA
366404
bpy
D216305
dBbpy
515477
dMebpy
569593
(18)
(19)
(20)
Octyl-PMI
752592
(Slow)*
More Cu Required
(14)
(15)
(16)
(17)
PMDETA
369497
Octadecyl-PMI
754420
High PDI
Control
Butyl-PMI
752606
Dodecyl-PMI
754412
Low PDI
Figure 3. The equilibrium constant KATRP plotted against kdeact illustrates the correlation
between catalyst activity and control. This should only be used as a reference, and was
adapted from Tang, W. et al.32 Each ligand is labeled with an acronym as well as the
Aldrich product number. Bidentate ligands are represented by blue diamonds, red
triangles represent tridentate ligands, and green squares represent tetradentate ligands.
*At a given concentration of catalyst, the activity axis shows the relative speed of the
polymerization reaction.
The perfect ATRP catalyst would be both fast and well controlled, but
this figure can help illustrate the relationship. If minimizing copper
concentration is the highest priority, then selecting catalysts from the
top of Figure 3 would be ideal. If a narrow distribution of chain lengths
(low PDI) is the highest priority, then the ideal catalyst would be selected
from the right side of the Figure 3.
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
(31)
(32)
Kamigaito, M.; Ando, T.; Sawamoto, M. Chem. Rec. 2004, 4, 159.

Edmondson, S.; Osborne, V. L.; Huck, W. T. S. Chem. Soc. Rev. 2004, 33, 14.
Matyjaszewski, K., Advances in Controlled/Living Radical Polymerization. American
Chemical Society: Washington, DC, 2003.
Hawker, C. J.; Bosman, A. W.; Harth, E. Chem. Rev. 2001, 101, 3661.
Benoit, D.; Chaplinski, V.; Braslau, R.; Hawker, C. J. J. Am. Chem. Soc. 1999, 121, 3904.
Hawker, C. J.; Barclay, G. G.; Orellana, A.; Dao, J.; Devonport, W. Macromolecules 1996,
29, 5245.
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Yamada, B. Macromolecules 1996, 29, 6393.
Chong, Y. K.; Krstina, J.; Le, T. P. T.; Moad, G.; Postma, A.; Rizzardo, E.; Thang, S. H.
Coote, M. L. J. Phys. Chem. A 2005, 109, 1230.
Achilleos, M.; Legge, T. M.; Perrier, S.; Patrickios, C. S. J. Polym. Sci., Part A: Polym. Chem.
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Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901.
Kabachii, Y. A.; Kochev, S. Y.; Bronstein, L. M.; Blagodatskikh, I. B.; Valetsky, P. M.
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Polym. Chem. 2002, 40, 2033.
Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1999, 32, 6877.
Matyjaszewski, K.; Wei, M.; Xia, J.; McDermott, N. E. Macromolecules 1997, 30, 8161.
OReilly, R. K.; Gibson, V. C.; White, A. J. P.; Williams, D. J. Polyhedron 2004, 23, 2921.
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188.
Wang, B.; Zhuang, Y.; Luo, X.; Xu, S.; Zhou, X. Macromolecules 2003, 36, 9684.
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Uegaki, H.; Kamigaito, M.; Sawamoto, M. J. Polym. Sci., Part A: Polym. Chem. 1999, 37,
3003.
Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1998, 31, 6756.
Brandts, J. A. M.; van de Geijn, P.; van Faassen, E. E.; Boersma, J.; Van Koten, G. J.
Organomet. Chem. 1999, 584, 246.
Le Grognec, E.; Claverie, J.; Poli, R. J. Am. Chem. Soc. 2001, 123, 9513.
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2005, 127, 5946.
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9994.
Terashima, T.; Ouchi, M.; Ando, T.; Sawamoto, M. J. Polym. Sci., Part A: Polym. Chem.
2010, 48, 373.
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43, 5595.
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3665.
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7631.
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Braunecker, W. A.; Itami, Y.; Matyjaszewski, K. Macromolecules 2005, 38, 9402.
Tang, W.; Kwak, Y.; Braunecker, W.; Tsarevsky, N. V.; Coote, M. L.; Matyjaszewski, K. J.
Am. Chem. Soc. 2008, 130, 10702.
The various ATRP techniques provide an opportunity to select a

polymerization environment that is well suited to meet applicationspecific needs. When used in combination with the ideal catalyst for a
given polymerization, well-defined polymers can be conveniently
prepared.
Aldrich.com
ATRP
Dave Haddleton
University of Warwick
Department of Chemistry
Background
Emergence of living radical polymerization mediated by transition metal
catalysts in 1995 was a seminal piece of work in the field of synthetic
polymer chemistry.1-3 Since this date, many transition metal complexes
have been shown to be effective with many different ligands and
transition metals. One is left with a number of dilemmas:
Which system should I use?
What reaction conditions should I start with?
Does it make any difference?
Alkyl Pyridylmethanimine Ligands
As with all effective types of transition metal catalytic processes, the

chemistry works due to facile interchange of the oxidation states of the
metal, which is controlled by the ligands on the metal.2 Although the
exact mechanism of atom transfer radical polymerization (ATRP) is
complex, and more than likely depends on the different ligands
employed, it can be simplified to a reversible redox system, whereby the
transition metal undergoes a reversible one electron oxidation and
reduction process, as shown in Figure 1.
kact
R X + Mtn-Y/Ligand
kdeact
Rn .
kp
+
kt
Note what happens when copper(0) (d10 s1) is left exposed to air on a
copper roof or in a bronze statue it oxidizes to a pale green copper(II).
Copper(I) is d10 with no readily available d-d transition and thus its
compounds are generally colorless, unless there is metal-ligand charge
transfer available. The practitioner of ATRP knows very well that even if
they purchase 99.999% pure Cu(I)Br from a commercial source it will
come as a pale green powder, due to trace oxidation to copper(II)
bromide. Also, during the course of a polymerization utilizing an alkyl
amine ligand [e.g., TREN (Aldrich Prod. No. 225630), Me6TREN (Aldrich
Prod. No. 723142), PMDETA (Aldrich Prod. No. 369497)] the solution
will often be a blue/green color. Since the resulting polymer normally
has the desired Mn and narrow PDI, this is often overlooked as the
reactions are undoubtedly very successful. However, it is indicative of a
build up of copper(II) complexes during the reaction. The second most
important part of the equilibrium is the stability of the polymer radical,
which changes depending on the electronic and steric environment. For
example, in a comparison between a propagating methacrylate and
acrylate polymer radicals, the methacrylate has an electron-donating
methyl group that also introduces steric effects; these effects are most
documented for large differences in propagating rate constants, kp.
X-Mtn+1-Y/Ligand
termination
Figure 1. Simplified mechanism for ATRP
Even though many different complexes have been shown to be

effective in ATRP, by far the most commonly used chemistry involves
copper(I) complexes based on a range of N-donor ligands.2 The role of
these ligands is often described as controlling the solubility of copper(I).
Those who have carried out ATRP with an aliphatic amine ligand or
bipyridine will know these reactions are quite often heterogeneous and
in some cases there is a considerable amount of insoluble material in the
reaction flask. However, even though the solubility of the catalyst is very
important, the role of the ligand is critical. If the reaction equilibrium lies
too far to the left the alkyl halide will be stable and unable to participate
in polymerization. Conversely, if the equilibrium is pushed too far to the
right, then a high concentration of free radicals will lead to conventional
free radical polymerization with termination by normal radical-radical
coupling, and in some cases disproportionation. The relative stabilities of
copper(I) and copper(II) complexes control the position of this
equilibrium and thus the electronic, and often the steric, nature of
the ligands in turn allows the synthetic chemist to control the
reaction. Copper(II) is usually more stable than copper(I). Copper(II)
is d9 which gives rise to characteristic blue and green complexes.
Alkyl pyridylmethanimine ligands were first used in 19964-11 as work

showed that these ligands readily form tetrahedral copper(I) complexes
which are unusually stable with regards to oxidation.12,13 The ligands are
very simply prepared by a condensation reaction exemplified by the
following procedure; 2-pyridine carboxaldehyde (20 mL, 0.21 mol) and
diethyl ether (20 mL) are added to a flask containing dried magnesium
sulfate (5 g). The flask is cooled to 0 C and n-propylamine (19 mL,
0.25 moles) added slowly. The mixture is removed from the ice bath and
stirred for two hours at 25 C prior to filtration. Diethyl ether is removed
by rotary evaporation and the resulting yellow oil purified by vacuum
distillation. The product is obtained as a straw-colored oil (bp. 43 oC at
7 10-2 mbar), with a 98% yield (Figure 2). The reaction occurs very
rapidly under these conditions and a point to note is that the resulting
Schiff bases are very stable towards hydrolysis even though the alkyl
groups have a primary carbon in the imine. This is contrary to many
organic text books that often state secondary or tertiary carbons are
required to prevent the reverse reaction. Note that in order to prepare
the methyl ligand, a 40% solution of methylamine in water (Aldrich
Prod. No. 426466) is needed for the reaction to proceed rapidly to
completion. This unexpected behavior led us for many months to avoid
primary amines, and the use of secondary and tertiary amines leads to
ligands that give relatively broad PDI polymers!
O
R NH2
N
H
Et2O, MgSO4
Copper(I)-mediated Living Radical

Polymerization in the Presence of Pyridylmethanimine Ligands
Copper(I)-mediated Living Radical Polymerization in the Presence of

Pyridylmethanimine Ligands
0C
Figure 2. Schematic of the synthesis of alkyl pyridylmethanimine
The alkyl pyridylmethanimine ligands have a very low lying * orbital

which readily accepts electron density from the copper(I).13 The
implication of this is that when copper(I) is complexed with two alkyl
pyridylmethanimine ligands, although the formal oxidation state of
copper is +1, in reality this is not the real oxidation state, or electron
content of the metal. In addition, the tetrahedral arrangement of the
ligand (Figure 3) shows that the access to the metal is restricted due to
Copper(I)-mediated Living Radical

Polymerization in the Presence of Pyridylmethanimine Ligands
ATRP
the steric bulk of the ligands.14-15 The combination of these effects is to
stabilize copper(I) towards oxidation such that it is even possible to
bubble air through a solution without causing oxidation.
Typical Reaction Conditions
Up to 66 weight % solids
Range of solvents from water and alcohols to toluene and cyclic ethers
60-80 C
Inert atmosphere, usually nitrogen
Robust to many different types of functional group19-21
Summary
Figure 3. Crystal structure of [L2Cu]Br, with L = N-ethyl 2-pyridylmethanimine.
In addition to the ligands complexing in a tetrahedral way during

polymerization, the monomer can act as a competing ligand (Figure 4).
This will occur for all methacrylates and acrylates, which inherently
contain good coordinating groups. This is most profound with tertiary
amine-containing ligands which result in competitive binding that can
be observed by a small change in reactivity ratios when compared to
free radical polymerization values.
O
N
Cu
N
N
R
N
R
O
O
Cu
N
N
N
R
Figure 4. Equilibrium involving DMAEMA (Aldrich Prod. No. 234907) / N-propyl 2-pyridyl
methanimine / copper(I) complexes.
It must be remembered that the copper complex formed with all ligand
types is always a salt with the transition metal complex forming the
cation. This can produce a solubility problem in non-polar solvents. Alkyl
pyridylmethanimine ligands help circumvent this by allowing for a facile
change in the alkyl group. As the alkyl chain is lengthened, the solubility
in non-polar solvents increases. For non-polar monomers such as
long chain acrylates and styrene, longer chain ligands need to be used
(n-butyl, n-pentyl, n-octyl). However, for polar monomers, it is desirable
to use the smallest alkyl chain possible for atom economy, and
purification reasons. An interesting, but very useful consequence of this
solubility is that during polymerization at high solids the polarity of the
reaction medium will decrease markedly. Thus, during the polymerization of methyl methacrylate (MMA) at 30-50% solids the polarity
decreases and often the catalyst will precipitate from solution, generally
as a highly colored oil throughout. This can be avoided by the use of a
more non-polar ligand with a longer alkyl group.
However, this potential problem can also have a positive effect with
regards to catalyst removal, which can be cited as an unfortunate aspect
of ATRP. The solubility of these ligands decreases as the polymerization
progresses and upon lowering the temperature from reaction temperature (typically 60-80 C) to ambient. This can result in almost complete
precipitation of the catalyst as sticky oil which adheres to the reactor,
allowing the catalyst to be removed via trituration/decanting. Alternatively, the reaction mixture can be filtered through a small column/
pad of fine filter agents such as Celite, basic alumina, basic silica which
remove the particulate catalyst, ligand and complex, since they adhere
to the medium. It is noted that care needs to be taken with certain
polymers which might also complex with the filtration medium.
Aldrich.com
The family of N-alkyl-2-pyridylmethanimines offers an alternative to

aliphatic amine ligands and bipyridine for copper(I)-mediated living
radical polymerization or ATRP. They yield very stable copper(I) which
allows for excellent polymerization of most methacrylate monomers in
polar and non-polar solvents. There is little evidence of oxidation or
disproportionation even with the most polar monomers and in the most
polar solvents16-17 which is often the case for the aliphatic amine type
ligands.18 Preparation of the ligands and their use in methacrylate
polymerization is facile. Typically more than 80% of researchers will
achieve polymers with PDI <1.20.
References
R = alkyl group
10
Polymerization is typically carried out under an inert atmosphere with

reagents being freeze, pump, thaw degassed. However, on scale-up it is
acceptable to bubble nitrogen through the reagents for 15-30 minutes
or to heat under nitrogen; 100 kg of MMA has been polymerized
effectively in this way.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
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Becer, C. R.; Haddleton, D. M. Polym. Chem. 2010, 1, 1086.
Percec, V.; Guliashvili, T.; Ladislaw, J. S.; Wistrand, A.; Stjerndahl, A.; Sienkowska, M. J.;
Monteiro, M. J.; Sahoo, S. J. Am. Chem. Soc. 2006, 128, 14156.
Ladmiral, V.; Mantovani, G.; Clarkson, G. J.; Cauet, S.; Irwin, J. L.; Haddleton, D. M. J. Am.
Chem. Soc. 2006, 128, 4823.
Nicolas, J.; Mantovani, G.; Haddleton, D. M. Macromol. Rapid Commun. 2007, 28,
1083.
Marsh, A.; Khan, A.; Haddleton, D. M.; Hannon, M. J. Macromolecules 1999, 32, 8725.
ATRP
Typical Procedures for Polymerizing via ATRP
Methylmethacrylate (MMA) Polymerization with

N-propyl-2-pyridylmethanimine
Styrene Polymerization with N-pentyl

2-pyridyl methanimine
Br
Br
n
CuBr, 1b
O
+
toluene, 110 C
EtO
CO2Et
Br
Br
O
EtO
CuBr, 1a
toluene, 90 C EtO
MeO
N
CO2Me
Figure 1. Polymerization of methylmethacrylate (MMA) with N-propyl-2-pyridylmethanimine, where 1a = N-propyl-2-pyridylmethanimine
The polymerization is carried out under oxygen free conditions. First the
transition metal salt is deoxygenated and then the solution, followed by
adding initiator to start the polymerization:
1) Cu(I)Br (0.134 g, 9.32 10-4 moles, Aldrich Prod. No. 212865)
and a dry magnetic stir bar were added to a dry Schlenk flask (or
round-bottom flask).
2) The tube is sealed with a rubber septum and deoxygenated with
three freeze, pump, thaw cycles using N2.
3) The polymerization solution was prepared by adding the following
reagents/solvents to the flask under N2:
Toluene (10 mL)
MMA (10 mL, 9.36 10-2 moles, Aldrich Prod. No. M55909)
N-propyl-2-pyridylmethanimine (0.279 g, 1.87 10-3 moles)
4) The Schlenk tube is subjected to three additional freeze, pump, thaw
cycles and then subsequently heated to 90 C with constant stirring.
5) Once the reaction temperature is reached the initiator ethyl2-bromoisobutyrate (0.136 mL, 9.36 10-4 moles, Aldrich Prod. No.
E14403) is added under N2 (t = 0) and the polymerization reaction
begins.
Figure 2. Polymerization of styrene with N-pentyl-2-pyridylmethanimine,

where 1b = N-pentyl-2-pyridylmethanimine
The polymerization is carried out under oxygen free conditions. First the
transition metal salt is deoxygenated, and then the monomer and
initiator are added to the solution and deoxygenated, followed by
adding ligand to start the polymerization:
1) Cu(I)Br (0.131 g, 9.1 10-4 moles) and a dry magnetic stir bar were
added to a dry Schlenk flask (or round-bottom flask).
Typical Procedures for Polymerizing via ATRP
The following two procedures describe two ATRP polymerization reactions

as performed by Prof. Dave Hadddletons research group at the
University of Warwick.
2) The tube is sealed with a rubber septum and deoxygenated with

three freeze, pump, thaw cycles using N2.
3) The polymerization solution was prepared as follows by adding the
following to the flask under N2:
Xylene (20 mL)
Styrene (10 mL, 8.73 10-2 moles, Aldrich Prod. No. 240869)
Ethyl-2-bromoisobutyrate (0.13 mL, 9.1 10-4 mol)
4) The flask is subjected to an additional three freeze, pump, thaw cycles
and subsequently heated to 110 oC with constant stirring.
5) Once the reaction temperature is reached, N-pentyl-2-pyridylmethanimine (0.28 mL, 1.8 10-3 mol) is added under N2 (t = 0).
Samples can be removed at 30-60 minute intervals using a degassed
syringe and analysed by GC or NMR for conversion and SEC for
molecular weight and polydispersity (PDI). The reaction was stopped
after 360 minutes, with a final conversion of 77.9 %. Mn = 5,270
(theoretical Mn = 7,900 g mol-1), PDI = 1.29.
Samples can be removed at 30-60 minute intervals using a degassed

syringe and analyzed by GC or NMR to determine the extent of
conversion and SEC for molecular weight and polydispersity (PDI).
After 300 minutes, the poly(methylmethacrylate) (PMMA) is isolated
with a final conversion of 89.3 %. Mn = 8,760 g mol-1 (theoretical
Mn = 8,930 g mol-1), PDI = 1.20.
11
Applying ARGET ATRP to the Growth of

Polymer Brush Thin Films by Surface-initiated Polymerization
ATRP
Applying ARGET ATRP to the Growth of Polymer Brush Thin Films

by Surface-initiated Polymerization
In this article, we will discuss ARGET ATRP, particularly focusing on the
application of this technique to surface-initiated polymerization (SIP).
This case study provides an excellent example of how using ARGET ATRP
in place of conventional ATRP can help to broaden the applicability and
appeal of a polymerization process.
Bocheng Zhu and Steve Edmondson*

Department of Materials, Loughborough University, Loughborough, LE11 3TU, UK
Introduction
In 2006, Matyjaszewski and co-workers first described controlled radical
polymerization by Activators ReGenerated by Electron Transfer Atom
Transfer Radical Polymerization (ARGET ATRP),1-3 a development of the
very widely used ATRP technology. ARGET ATRP offers two principle
advantages over conventional ATRP: improved tolerance of oxygen and
significantly reduced heavy metal catalyst concentrations.
Polymerization initiator site

Surface-binding site
Initiator molecule
Surface
Initiator
attachment
We will first introduce SIP and explore why controlled radical polymerization (CRP) in general, and ATRP in particular, has become such a
popular choice of polymerization technology for SIP. After introducing
ARGET ATRP, we will discuss how it enables SIP to be more widely
applied outside of the synthetic chemistry laboratory.
Surface-initiated Polymerization (SIP) and

Polymer Brushes
Chain-growth polymerizations (e.g., radical addition polymerization)
frequently use initiators intimately mixed with the monomers either in
solution or in bulk. However, if initiators can be tethered to a surface
(using established chemistry from the field of self-assembled
monolayers),4 then chains grown from these initiators will also be endtethered (or grafted) to the surface. Such a process is termed surfaceinitiated polymerization (SIP). The overall process for SIP is shown in
Figure 1.
Strongly grafted thin polymer film
polymer brushes
Surface-initiated
polymerization
Monomer,
Catalyst
Figure 1. The process for generating a polymer brush. First, initiator molecules are attached to a surface, then in the presence of monomer and catalyst the polymer
chains are grown from the surface.
12
Using initiator molecules with specific surface-binding groups (e.g.,

thiols, silanes, or catechols), monolayers containing a high density of
initiator sites can be produced. When polymerization is initiated from a
fraction of these sites (the exact fraction depending on the polymerization system and conditions), a layer of densely-packed chains is
produced, known as polymer brushes. Experimentally, such polymerizations are conducted by immersing an initiator-functionalized surface
into bulk monomer or monomer solution, with additional components
such as catalysts and free (untethered) initiator added depending on the
exact polymerization type.
Controlled Radical Polymerization for SIP
From an applications perspective, these coatings can be considered as

ultra-thin (typically 0-500 nm) polymer films with outstanding stability
towards solvents due to covalent chain tethering. These films can be
immersed in a good solvent for the polymer without fear of damage or
dissolution. The coating will reversibly swell in a good solvent, an effect
which can be utilized for sensing applications.5 This solvent stability has
been particularly well-exploited in producing robust coatings of
hydrophilic polymers, with applications such as non-biofouling/proteinresistant surfaces6 and antimicrobial coatings7 for proposed use in
biosensors and medical devices. In addition, the bottom-up nature of
the polymer growth allows thin films to be produced free of pin-hole
defects commonly encountered with spin-coating, and makes them
suitable for use as dielectric layers in electronic devices.8 Furthermore,
patterning these polymer layers is simple, requiring only that the initiator
layer is generated using any of the existing well-developed monolayer
patterning techniques (e.g., micro-contact printing).9
Using CRP allows the molecular weight of the grafted chains to be easily
controlled, which in turn controls the thickness of the brush layer.
Perhaps the simplest way of achieving this control is to vary the
polymerization time experimentally, this can be realized by simply
removing samples from the reaction periodically as required. Very thin
uniform films (just a few nanometers thick) can be produced in this way
using slow polymerization methods and short growth times, although
thicknesses of up to ~500 nm are possible. Gradients of thickness can
also be produced by slowly feeding polymerization solution (monomer
and catalyst in solvent) into or out of the vessel containing the
substrate.12 Thickness control can also be achieved by adding free
(untethered) initiator and allowing the polymerization to run to high
conversion, with the molecular weight being determined by the
[monomer]/[initiator] ratio. However, this method produces free polymer
which can make sample extraction and cleaning difficult.
Aldrich.com
Most chain-growth polymerization techniques which have been utilized

to synthesize polymers in bulk or in solution have also been applied to
growing polymer brushes. However, the vast majority of recent research
in coatings has focused on CRP technology such as nitroxide-mediated
polymerization (NMP), reversible addition/fragmentation chain transfer
polymerization (RAFT) and most notable ATRP. For detailed coverage of
the application of CRP to polymer brush growth, see reviews by
Edmondson et al.10 and Barbey et al.11
ATRP
0500 nm
High-quality thin films
Multilayer films
ARGET ATRP for Robust Brush Growth

ATRP has been very successfully used for surface-initiated polymerization, but suffers one major drawback the oxygen sensitivity of the
Cu(I) complexes typically used for polymerization. This sensitivity
necessitates careful deoxygenation of solvents and polymerization
vessels. Matyjaszewski and co-workers have recently developed a version
of ATRP, termed ARGET ATRP which has greatly reduced sensitivity to
oxygen by the introduction of an excess of reducing agent in the
reaction.1-3
Reducing Agent
Thickness gradients
Cu(I)
Patterned films
Figure 2. Examples of the diverse film structures which can be produced by surfaceinitiated polymerization.
ATRP
Cu(II)
Oxygen
ATRP has proved to be the most popular CRP technology for the
formation of polymer brushes, with hundreds of published examples.
The beneficial features of ATRP for solution polymerization (e.g.,
tolerance to a wide range of functional groups, ability to polymerize at
room temperature in environmentally benign solvents with good
control) are also applicable to SIP brush growth. A wide range of
acrylates, methacrylates, and styrenic monomers have been used to
make brush coatings with surface-initiated ATRP. Many diverse classes of
polymers have been grown this way, including hydrophobic, hydrophilic, charged (cationic and anionic), stimuli-responsive (pH and
temperature), biocompatible, cell-adhesive, antimicrobial, and chemically
reactive (for post-growth functionalization or crosslinking).11
Figure 5. The fundamental reactions of ARGET ATRP. In the normal course of ATRP, the
catalyst is shuttled between the two oxidation states. The presence of excess reducing
agent counters the effect of oxygen (or other processes such as termination),
regenerating lost Cu(I).
In addition to the wide range of accessible polymer functionality,

the popularity of ATRP for SIP can also be attributed to the ease of
synthesis of suitable alkyl halide initiators. An acyl bromide initiator,
2-bromoisobutyryl bromide (BIBB) (Figure 3) is commercially available
(Aldrich Prod. No. 252271) and can be used to synthesize a range of
surface-reactive initiators such as silanes (for silica and some metal
oxides) and catechols (for some metal oxides). A disulfide-functional
initiator is also commercially available (Aldrich Prod. No. 733350 in
Figure 3) for use with noble metals (e.g., gold) and select oxide-free
transition metal surfaces (e.g., copper).
Copper catalyst can be added initially as Cu(II) and generate active

Cu(I) in situ via reduction at the start of the polymerization. Therefore,
only air-stable Cu(II) salts need to be stored and handled in the
laboratory, rather than air-sensitive Cu(I) salts.
The total amount of copper catalyst can be greatly reduced, even
down to ppm levels,1 since the polymerization rate theoretically only
depends on the ratio [Cu(I)] / [Cu(II)], not the total amount of copper.
Conventional ATRP must employ much greater concentrations of
copper than ARGET ATRP to minimize the effects of oxidation and
termination.
A)
B)
O
Br
O
O
S
Br
Br
Br
O
O
Figure 3. ATRP initiator 2-bromoisobutyryl bromide is commonly used to synthesize

functionalized initiators, and bis[2-(2-bromoisobutyryloxy)undecyl] disulfide is an ATRP
initiator that is used to functionalize noble metals and oxide-free transition metal
surfaces.
Surfaces bearing organic hydroxyl groups (C-OH) can be more directly

modified to incorporate initiating sites by directly reacting with BIBB, an
approach which has been used to functionalize surfaces such as
cellulose13 and oxidized/activated polymer surfaces (shown in Figure 4).
Our group has also been working on more general (non-substratespecific) initiators, based on polyelectrolytes14 and dopamine
polycondensation15 to further broaden the application of SIP.
O
OH
BIBB
Br
The effect of oxygen in a conventional ATRP polymerization is to oxidize

the Cu(I) to Cu(II). Since the polymerization rate is proportional to the
ratio [Cu(I)] / [Cu(II)], a small amount of oxygen leads to a large reduction
in polymerization rate. ARGET ATRP overcomes this problem by having a
reservoir of reducing agent in the reaction mixture. Cu(II) generated by
oxidation, or other processes such as termination or disproportionation,
is simply reduced back to the active Cu(I) (Figure 5).

A wide range of monomers have been utilized to prepare polymer

brushes via CRP. Some polymer brushes can also be modified after
growth, for example by coupling biomolecules, giving an even wider
range of available functionality. Moreover, multi-block copolymers
producing multi-layer films can also be made by sequential polymer
growth with different monomers (Figure 2).
ARGET ATRP offers further advantages over conventional ATRP:
The controlled synthesis of a range of polymers in solution (i.e., not

tethered) using ARGET ATRP have been reported, for example hydrophobic polymers such as polystyrene (PS),2 poly(methyl methacrylate)
(PMMA),1,3 and poly(n-butyl acrylate) (PnBA),1,3 as well as hydrophilic
poly(2-hydroxyethyl methacrylate) (PHEMA).16 The high level of control
possible with ARGET ATRP has been demonstrated by the synthesis of
block copolymers.1,3 In some cases ARGET ATRP allows the synthesis of
polymers that are not accessible by conventional ATRP, such as high
molecular weight acrylonitrile homopolymers17 and copolymers.18
Interestingly, some reported ARGET ATRP polymerizations do not require
the addition of a reducing agent, for example tertiary amine groups
present on the ligand19 or monomer (2-dimethylaminoethyl methacrylate, DMAEMA)20 can act as intrinsic reducing agents.
The benefits of ARGET ATRP over conventional ATRP make it a
particularly attractive system for the growth of polymer brushes by SIP.
The less stringent experimental conditions required make ARGET ATRP
ideal for use by scientists and engineers with all levels of synthetic
expertise, greatly broadening the application of polymer brush growth.
Furthermore, low catalyst concentrations, ambient temperature polymerization conditions (for many monomers) and relatively benign
solvents and reducing agents (e.g., methanol/water mixes and ascorbic
acid, respectively) make this technique more applicable for use outside
the chemistry laboratory, and extendable into industrial settings.
Figure 4. Introduction of ATRP initiator sites onto a hydroxyl-functional surface

(e.g., cellulose) using 2-bromoisobutyryl bromide (BIBB).
13

ATRP
Sample handling with ARGET ATRP is also simplified since it is sufficient
for the polymerization to be conducted in a sealed jar under air, because
the small amount of oxygen present will be consumed by the excess
reducing agent. However, to prepare polymer brush surfaces by
conventional ATRP the system must be enclosed in rigorously
deoxygenated flasks or entirely conducted in a glove box.
The tolerance of the polymerization to low levels of oxygen also allows
samples to be removed from a polymerization vessel during the reaction
without terminating the polymerization. Samples can even be analyzed
(e.g., ellipsometric thickness) and returned to the polymerization reaction
if a thicker layer is required. Conventional ATRP would require an
extensive process for re-initiation including transfer to a new deoxygenated reaction flask with fresh polymerization solution.
Research utilizing ARGET ATRP for surface initiated polymerization is
continuing to grow. Matyjaszewski and coworkers first demonstrated the
technique by synthesizing PnBA brushes and PnBA-block-PS copolymer
brushes.21 More recently, chemically functional polymer brushes such as
epoxy-functional poly(glycidyl methacrylate)13 and hydroxyl-functional
PHEMA15 have also been prepared by ARGET ATRP. In addition, PMMA
brushes via ARGET ATRP have been grown from a variety of substrate
materials including silicon wafers,15 high-surface-area porous silica,22 and
imogolite nanotubes (an aluminosilicate clay).23
Our group has had significant success in simply adapting existing ATRP
protocols into ARGET ATRP protocols, especially those run at ambient
temperature using polar solvents (e.g., methanol and water), by simply
applying the following algorithm:
Monomer and solvents quantities are kept identical
Replace Cu(I) salts with CuBr2 and greatly reduce the overall copper
concentration. (Typical [monomer]:[Cu] = 5000:1)
Keep the same ligand species, but increase the amount of ligand.
(Typical [ligand]:[Cu] = 10:1)
Add reducing agent (typically ascorbic acid or sodium ascorbate), in
large excess over copper. (Typical [reducing agent]:[Cu] = 10:1)
To conduct ARGET ATRP in the most ideal manner (achieving the best
control and the lowest polydispersity), further optimizations need to be
made. For example, a stronger chelating ligand (e.g., Me6TREN or TPMA)1
may need to be used and the concentration and nature of the reducing
agent should be optimized. However, in surface-initiated polymerization
a simple recipe produced by the algorithm above is often sufficient to
grow a brush layer, where polydispersity and good re-initiation efficiency
are not of critical importance. A typical polymerization procedure for
PMMA brushes, developed using this algorithm, is given at the end of
this article.
Conclusion
In this short article, we have reviewed the fundamental principles of
ARGET ATRP and discussed the advantages of this technique over
conventional ATRP. We have focused on the application of ARGET ATRP
for surface-initiated polymerization to prepare polymer brushes. Using
ARGET ATRP in this application reduces the experimental complexity of
brush growth, in particular by requiring less rigorous inert atmosphere
conditions. The synthesis of a range of useful polymers (both surfacetethered and free) by ARGET ATRP has been demonstrated in literature,
and this useful technique is likely to grow in importance for controlled
polymer synthesis both inside and beyond the chemistry laboratory.
References
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
Matyjaszewski, K. Jakubowski, W. Min, K. Tang, W. Huang, J. Braunecker, W. A.;

Tsarevsky, N. V. Proc. Natl. Acad. Sci. 2006, 103, 15309.
Jakubowski, W. Min, K.; Matyjaszewski, K. Macromolecules 2006, 39, 39.
Jakubowski, W.; Matyjaszewski, K. Angewandte Chemie 2006, 118, 4594.
Ulman, A. Chemical Reviews 1996, 96, 1533.
Fielding, L. A. Edmondson, S.; Armes, S. P. Journal of Materials Chemistry 2011, 21,
11773.
Feng, W. Brash, J. L.; Zhu, S. Biomaterials 2006, 27, 847.
Xu, F. J. Yuan, S. J. Pehkonen, S. O. Kang, E. T.; Neoh, K. G. I. Nanobiotechnology 2006,
2, 123.
Pinto, J. C. Whiting, G. L. Khodabakhsh, S. Torre, L. Rodrguez, a; Dalgliesh, R. M.
Higgins, a M. Andreasen, J. W. Nielsen, M. M. Geoghegan, M. Huck, W. T. S.;
Sirringhaus, H. Advanced Functional Materials 2008, 18, 36.
Xia, Y.; Whitesides, G. M. Advanced Materials 2004, 16, 1245.
Edmondson, S. Osborne, V. L.; Huck, W. T. S. Chemical Society Reviews 2004, 33, 14.
Barbey, R. Lavanant, L. Paripovic, D. Schwer, N. Sugnaux, C. Tugulu, S.; Klok, H.-A.
Chemical Reviews 2009, 109, 5437.
Bhat, R. R. Tomlinson, M. R.; Genzer, J. Journal of Polymer Science Part B: Polymer
Physics 2005, 43, 3384.
Hansson, S. Ostmark, E. Carlmark, A.; Malmstrom, E. ACS Applied Materials &
Interfaces 2009, 1, 2651.
Edmondson, S.; Armes, S. P. Polymer International 2009, 58, 307.
Zhu, B.; Edmondson, S. Polymer 2011, 52, 2141.
Paterson, S. M. Brown, D. H. Chirila, T. V. Keen, I. Whittaker, A. K.; Baker, M. V. J. Polym.
Sci. Pol. Chem. 2010, 48, 4084.
Dong, H. Tang, W.; Matyjaszewski, K. Macromolecules 2007, 40, 2974.
Pietrasik, J. Dong, H.; Matyjaszewski, K. Macromolecules 2006, 39, 6384.
Kwak, Y.; Matyjaszewski, K. Polymer International 2009, 58, 242.
Dong, H.; Matyjaszewski, K. Macromolecules 2008, 41, 6868.
Matyjaszewski, K. Dong, H. Jakubowski, W. Pietrasik, J.; Kusumo, A. Langmuir 2007, 23,
4528.
Cao, L.; Kruk, M. Polymer Chemistry 2010, 1, 97.
Ma, W. Otsuka, H.; Takahara, A. Chemical Communications 2011, 47, 5813.
Lao, H.-K. Renard, E. El Fagui, A. Langlois, V. Valle-Rehel, K.; Linossier, I. Journal of
Applied Polymer Science 2011, 120, 184.
It should be noted that if an ARGET ATRP brush growth protocol

produces brush layers which are too thin, as measured by ellipsometry
or other techniques, this could occur for two quite different reasons:
The polymerization is too fast, causing high levels of termination. In
this case, the polymerization can be slowed by using less polar
solvents or less active reducing agents.
The polymerization is too slow. In this case, the polymerization can be
accelerated by using more polar solvents (e.g., adding water to the
solvent mix), more active reducing agents, or adopting more rigorous
oxygen exclusion.
These two scenarios can be differentiated by growing samples for a
range of times, making obvious the difference between early
termination (constant thickness with increasing time) and slow
propagation (slowly increasing thickness).
14
Aldrich.com
ATRP
ARGET ATRP: Procedure for PMMA Polymer Brush Growth

After annealing, substrates can be reacted directly with BIBB, using the
same procedure as for cellulose, above.
Initiator-coated substrates can be stored in air for several weeks without
significant loss of activity.
Surface Cleaning and Initiator Immobilization
EtO
APTES
EtO Si
EtO
Surface preparation before polymer brush growth consists of two steps:

surface cleaning and initiator monolayer deposition.
There are many common techniques for rigorous surface cleaning;
however, the choice is dependent on substrate type, the degree of
contamination, and the desired cleanliness of the surface. Heavily
contaminated inorganic substrates can be cleaned by washing and
ultrasonication in aqueous surfactants and solvents, followed by
immersion in piranha solution (H2O + H2O2 + H2SO4 warning,
extremely hazardous). Silica surfaces (including silicon wafers) can be
cleaned using the less hazardous RCA-1 clean (H2O + H2O2 + NH4OH)
in place of piranha solution, which introduces silanol (Si-OH) groups to
the wafer surface to allow reaction with silanes. For less heavily
contaminated inorganic surfaces, a dry clean using UV/O3 exposure will
often suffice.
Organic surfaces such as polymers or cellulose are often cleaned simply
using solvents. If the material does not intrinsically contain nucleophilic
amine or hydroxyl groups, the surface can be activated by a variety of
means (e.g., UV/O3 or O2 plasma to introduce hydroxyl groups,
treatment of polyesters with ethylenediamine to introduce amine
groups).24
After the surface is clean the initiator monolayer can be formed using a
method specific to the surface type.
1) Gold and other noble metals surfaces:Monolayers of initiator can
be formed by simply immersing the surface in a dilute solution of a
disulfide initiator (Aldrich Prod. No. 733350) (1-5 mM in ethanol) for 1624 hours under ambient conditions, followed by washing with ethanol.
2) Organic hydroxyl functional surfaces (e.g., cellulose or activated
polymer surfaces): ATRP initiator sites are introduced by reacting
surface hydroxyls or amines with 2-bromoisobutyryl bromide (BIBB,
Aldrich Prod. No. 252271) in anhydrous solvent with an amine base. A
typical procedure for cellulose is given below:
Cellulose (fibers or paper) is placed in a test tube sealed with a septum
and the tube deoxygenated by nitrogen purging or vacuum/nitrogen
cycling.
Anhydrous tetrahydrofuran (THF, 10 mL, Aldrich Prod. No. 401757) is
syringed over the cellulose. BIBB (0.26 mL, 2.10 mmol) and anhydrous
triethylamine (0.30 mL, 2.10 mmol) are added by syringe and the tube
gently agitated to mix. Note: triethylamine should be dried using 4
molecular sieves before use.
After 1 hour remove the cellulose from the tube, wash with THF,
methanol and deionized water and then dry under a nitrogen stream.
3) Silica/silicon and other metal oxides: Many publications use presynthesized silane ATRP initiators for these surfaces. However, a
procedure suitable for all levels of synthetic expertise is provided below
(and illustrated in Figure 1), using only commercial reagents:
Clean substrates are placed in a vacuum desiccator or vacuum oven
with a vial containing 10 drops of (3-aminopropyl)triethoxysilane
(APTES, Aldrich Prod. No. A3648). The chamber is then pumped down
to <1 mbar, isolated from the pump and left under vacuum for
30 minutes.
Substrates are then annealed at 110 C in air at atmospheric pressure
for 30 minutes. Note: if using the same vacuum oven for both steps,
remove the APTES before heating.
Si/SiO2
NH2
O
Si/SiO2
OH
NH2
Si
O
BIBB, Et3N
THF
H
O
Si/SiO2
Br
Si
O
Silane Initiator
Figure 1. Surface functionalization with silane ATRP initiator.
Polymer Brush Growth by ARGET ATRP

A typical procedure for the growth of PMMA polymer brushes is given
below, and illustrated in Figure 2.
O
Bocheng Zhu and Steve Edmondson*

Department of Materials
Loughborough University, Loughborough, LE11 3TU, UK
MMA, MeOH, H2O

Br
bpy, ascorbic acid

CuBr2
Br
Figure 2. Polymerization of methyl methacrylate from a surface.
Samples can be handled using stringent inert atmosphere with the

polymerization taking place in a deoxygenated tube or under less
stringent conditions in a screw-top jar (Figure 3). Several ARGET ATRP
brush growth polymerization methods will work adequately under the
less stringent conditions, which also greatly simplifies handling. Under
less stringent conditions fresh samples can simply be dipped into the
solution and removed when desired, although the jar should be sealed
for the majority of the polymerization time.
N2
N2
Stopper with
septum
Needle
Polymer-coated
substrate
Add CuBr2, bpy,
ascorbic acid
Magnetic
stirrer bar
Deoxygenate monomer/solvent
solution with nitrogen bubbling
Stir to dissolve while

purging headspace
Polymerization solution syringed

into deoxygenated tube or poured
into screw-top jar, which is then
capped
OR
Substrate in deoxygenated tube (more stringent)

or screw-top jar (less stringent)
Samples removed
and washed
OR
Grow polymer for desired time

(typically up to 24 hours)
Figure 3. Typical experimental procedure for SIP by ARGET ATRP.
Initiator-coated substrates are placed in test tubes which are

deoxygenated by nitrogen purging or vacuum/nitrogen cycling.
Alternatively, they can be placed in a screw-top jar under air.
In a round-bottomed flask sealed with a septum, methanol (16 mL),
water (4 mL) and methyl methacrylate (20 mL, 18.72 g, 187.0 mmol,
Aldrich. Prod. No. M55909) are mixed and deoxygenated by bubbling
through nitrogen for 10-15 minutes.
15
CuBr2 (7.4 mg, 0.033 mmol, Aldrich Prod. No. 221775), 2,2-dipyridyl
(bpy, 51.5 mg, 0.33 mmol, Aldrich Prod. No. D216305) and sodium
L-ascorbate (65.3 mg, 0.33 mmol, Aldrich Prod. No. A7631) or ascorbic
acid (58.1 mg, 0.33 mmol, Aldrich Prod. No. A0278) are added and the
headspace purged with nitrogen. The mixture is stirred to dissolve the
solids.
The solution is syringed over the substrates in the deoxygenated
tubes, or simply poured over the substrates in the screw-top jar, which
is then resealed. The samples are allowed to polymerize at ambient
temperature.
After the desired polymerization time, samples are removed and
washed with methanol and water. If free polymer is observed on
the samples, this can be removed by washing with THF or other
appropriate solvents for PMMA the polymer coating will not be
damaged by solvent washing.
Typically, this method produces a polymer growth rate of approximately

10 nm/hour (Figure 4).
250
Polymer Thickness (nm)
ATRP
200
150
100
50
0
10
15
20
Polymerization Time (hours)
25
Figure 4. PMMA Polymer brush thickness during polymerization under stringent

deoxygenation conditions at 20 C (measured by ellipsometry).
ATRP Initiators
For a complete description of available ATRP initiators including purities, visit Aldrich.com/crp.
Name
Structure
tert-Butyl -bromoisobutyrate
CH3
H3C
O
CH3
H3C Br
CH3
Methyl -bromoisobutyrate
O
H3C
OCH3
Description
Prod. No.
Atom Transfer Radical Polymerization (ATRP) initiator with a

tert-butyl leaving group.
17455-100ML
17455-500ML
Atom Transfer Radical Polymerization (ATRP) initiator that

will generate a polymer with a methyl end group
17457-100ML
Br CH3
-Bromoisobutyryl bromide
Used to form an N-protected halodienamide which provided 252271-100G

four- and five-membered lactams in the presence of copper 252271-500G
(I) and a tertiary amine.
Atom Transfer Radical Polymerization (ATRP) initiator commonly used to functionalize alcohols or oxidized surfaces.
O
Br
H3C
Ethyl -bromoisobutyrate
Br
CH3

will generate a polymer with an ethyl end group.
O
H3C
CH3
Br CH3
2-Hydroxyethyl 2-bromoisobutyrate
Atom Transfer Radical Polymerization (ATRP) initiator for the 723150-1G

creation of hydroxy functionalized telechelic polymers. Can 723150-5G
be used to modify carboxylate- or isocyanate- modified
surfaces, particles, or biomolecules.
O
H3 C
Br
Ethylene bis(2-bromoisobutyrate)
OH
O
CH3
H3C
O
Br
H3C
1,1,1-Tris(2-bromoisobutyryloxymethyl)ethane
Br
CH3
O
CH3
Br CH3
O
H3C
O

723177-5G
creation of difunctional polymers.
Polymerization will occur at two sites creating a polymer
with ester functionality at the center.
CH3

723185-5G
creation of trifunctional polymers.
Polymerization will occur at three sites creating a three-arm
star polymer.
Br CH3
O
CH3
O
CH3
O
O
E14403-5G
E14403-100G
E14403-500G
Br CH3
Pentaerythritol tetrakis(2-bromoisobutyrate)
Br
CH3
O
O
O
H3 C
Br
O
CH3
H3 C
Br
Dipentaerythritol hexakis(2-bromoisobutyrate)
RO
O
O
CH3
OR
Br CH3
O
O
H3C
CH3
O
O
O
OCH2(CH2)9CH2S
SCH2(CH2)9CH2O
734586-1G
734586-5G

preparation of biodegradable polymers as well as polymers 723169-5G
that adhere to gold surfaces.
This can also be used to introduce temperature and light
sensitive regions to cleave the polymer.
CH3
Br
CH3
O
H3C
H3C Br
Aldrich.com
CH3
O
Br
16
CH2

723207-5G
creation of hexafunctional polymers.
Polymerization will occur at six sites creating a six-arm star
polymer.
Atom Transfer Radical Polymerization (ATRP) initiator with a
methacrylate functionality for branched polymerization,
orthogonal polymerization, or other functionalization.
H3C Br
H3C
CH3
R=*
OR
2-(2-Bromoisobutyryloxy)ethyl
methacrylate
Bis[2-(2-bromoisobutyryloxy)ethyl]disulfide
CH3
Br
CH3
OR
RO
RO
Bis[2-(2-bromoisobutyryloxy)undecyl] disulfide

723193-5G
creation of tetrafunctional polymers.
Polymerization will occur at four sites creating a four-arm star
polymer.
CH3
O
CH3
Br CH3
Atom Transfer Radical Polymerization (ATRP) initiator commonly used to functionalize noble metal surfaces. This can
also be used to introduce temperature and light sensitive
regions to cleave the polymer.
733350-500MG
ATRP
Name
Structure
10-Undecenyl 2-bromoisobutyrate
O
H3C
Dodecyl 2-bromoisobutyrate

creation of dodecyl functionalized telechelic polymers.
723223-5G
O
H3C
Prod. No.
723215-1G
723215-5G
OCH2(CH2)10CH3
H3C Br
Octadecyl 2-bromoisobutyrate

creation of stearyl functionalized telechelic polymers.
723231-5G
O
H3C
OCH2(CH2)16CH3
Br CH3
Poly(ethylene glycol) methyl ether

2-bromoisobutyrate
Average Mn: 2,200
Poly(ethylene glycol)-containing ATRP initiator for generat- 750069-1G

750069-5G
ing a block copolymer with a PEG block on one end. The
PEG block is terminated with an unreactive methoxy group.
Can be used to enhance biocompatibility.
O
H3CO
CH3
Br CH3
n

2-bromoisobutyrate
Average Mn: 5,000

736333-5G
O
H3CO
CH3
Ligands for ATRP Catalysts
OCH2(CH2)8CH CH2
Br CH3
Description
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.
Br CH3
n

2-bromoisobutyrate
Average Mn: 1,200

739456-5G
O
H3CO
CH3
Br CH3
n
Poly(ethylene glycol) bis(2-bromoisobutyrate)

Average Mn: 1,000
H3C Br
O
H3C
CH3
Poly(ethylene glycol)-containing ATRP initiator for generating a triblock copolymer with a PEG block in the center.
740888-1G
741019-1G
740896-1G
Br CH3

Average Mn: 2,200
H3C Br
O
H3C
CH3
Br CH3

Average Mn: 4,300
H3C Br
O
H3C
O
CH3
Br CH3
n

For a complete description of available ligands, visit Aldrich.com/crp.
Name
Structure
Prod. No.
D216305-2.5G
D216305-10G
D216305-25G
D216305-100G
D216305-500G
D216305-1KG
2,2-Bipyridyl
N
4,4-Dimethyl-2,2-dipyridyl
H 3C
4,4-Di-tert-butyl-2,2-dipyridyl
t-Bu
569593-1G
569593-5G
t-Bu
515477-5G
515477-25G
CH2(CH2)7CH3
482250-1G
482250-5G
4,4-Dinonyl-2,2-dipyridyl
CH3
CH3(CH2)7CH2
N-Butyl-2-pyridylmethanimine
752606-1G
N
CH3
752592-1G
N-Octyl-2-pyridylmethanimine
N
N-Dodecyl-N-(2-pyridylmethylene)amine
CH2(CH2)6CH3
754412-1ML
N
CH2(CH2)10CH3
N-Octadecyl-N-(2-pyridylmethylene)amine
754420-1G
N
N,N,N,N,N-Pentamethyldiethylenetriamine
CH2(CH2)16CH3
CH3
CH3
H3C
369497-250ML
369497-1L
CH3
CH3
17
ATRP
Name
Structure
Prod. No.
723134-250MG
723134-1G
Tris(2-pyridylmethyl)amine
N
N
1,1,4,7,10,10-Hexamethyltriethylenetetramine
H3C
CH3
N
N
CH3
Tris[2-(dimethylamino)ethyl]amine
H3 C
H3 C
CH3
N
CH3
366404-5G
366404-25G
723142-1ML
CH3
N
CH3
1,4,8,11-Tetraazacyclotetra-decane
CH3
N
CH3
N
CH3
259160-1G
259160-5G
NH HN
NH HN
1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane
H3C
N
CH3
N
N
H3C
N
CH3
N,N,N,N-Tetrakis(2-pyridylmethyl)ethylenediamine
282804-1G
N
N
N
P4413-50MG
P4413-100MG
N
N
Metal Salts for ATRP Catalysts

For a complete list of available metal salts, visit Aldrich.com/metalsalts.
Name
18
Purity
Prod. No.
Copper(I) chloride
CuCl
99.995% trace metals basis
229628-10G
229628-100G
Copper(II) chloride
CuCl2
203149-10G
203149-50G
Copper(I) bromide
CuBr
254185-10G
254185-100G
Copper(II) bromide
CuBr2
437867-5G
437867-25G
Titanium(II) chloride
TiCl2
451738-1G
451738-5G
Titanium(III) chloride
TiCl3
514381-1G
514381-5G
Titanium(IV) chloride
TiCl4
254312-10G
254312-50G
Titanium(IV) bromide
TiBr4
451606-1G
451606-5G
Iron(II) chloride
FeCl2
98%
372870-25G
372870-250G
Iron(III) chloride
FeCl3
451649-1G
451649-5G
Iron(II) bromide
FeBr2
98%
400831-10G
400831-50G
Iron(III) bromide
FeBr3
98%
217883-10G
217883-50G
Cobalt(II) chloride
CoCl2
97%
232696-5G
232696-100G
232696-500G
Cobalt(II) bromide
CoBr2
99%
334022-50G
334022-250G
Nickel(II) chloride
NiCl2
451193-5G
451193-25G
Nickel(II) bromide
NiBr2
449156-1G
449156-5G
Molybdenum(III) chloride
MoCl3
339334-2G
Molybdenum(V) chloride
MoCl5
642452-2G
642452-10G
Ruthenium(III) chloride
RuCl3
208523-2G
208523-10G
208523-50G
Aldrich.com
Formula
RAFT
A Micro Review of Reversible/Addition Fragmentation

Chain Transfer (RAFT) Polymerization
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 be comprised of
dormant chains.
Living (dormant)
chains
Introduction
dead chains
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, NR2, COOH, CONR2, SO3H). 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).
106
105
104
103
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
A Micro Review of 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
Weak single bond

R'
Reactive
double bond
S R
Z
kadd
R'
k-add
S R
Z
Z modifies addition and

fragmentation rates
R'
S + R
Z
R must be a good homolytic leaving

group and a good inititating species
Scheme 1. Mechanism for reversible addition-fragmentation chain transfer (RAFT)
ZC(=S)S RAFT ends

= dormant chains
Initiatorderived ends
Dead chains
'R' RAFT
ends
Propagating radicals
= active 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.
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), and styrene (St, Aldrich
Prod. No. S4972). 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).
19
RAFT
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
>
Me
~ Me >>
Me
> OPh > OEt ~
Me
> N(Et)2
N
H
MMA, HPMAM
VAc, NVP, NVC
A Micro Review of Reversible Addition/

St, MA, AM, AN

CH3
CH3
CH3
H
CH3
COOEt >>
R:
CN ~
Ph >
Ph >
CH2
CH3
CH3
CH3
CN
CH3
CH3
H
CH3
H
H
CH3
CN ~
Ph ~
CH3 ~
CH3 ~
CN ~
Ph
H
CH3
CH3
CH3
H
H
MMA, HPMAM
St, MA, AM, AN
VAc, NVP, NVC
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).
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)but2-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).
[RAFT]=0.003 M, Mn=125,000, =1.16
[RAFT]=0.006 M, Mn=84,000, =1.11
[RAFT]=0.012 M, Mn=39,600, =1.09
[RAFT]=0.025 M, Mn=20,600, =1.09
[RAFT]=0.05 M, Mn=9,300, =1.11
[RAFT]=0.10 M, Mn=4,600, =1.15
[RAFT]=0.20 M, Mn=2,600, =1.17
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 nanotechnology 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
S
106
105
CO2H
CN
CN
5
4
S S
S
C12H25S
C12H25S
SC12H25
S S
S
CN
6
7
S
S S
S S
CN
8
9
S
S
Ph
10
Figure 4. A series of RAFT agents that show good polymerization control for MAMs.
20
Aldrich.com
103
102
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
C12H25S
C12H25S
104
Molecular Weight (g/mol)
RAFT
RAFT Polymerization of Less-Activated
Monomers (LAMs)
Conclusions
Table 1. RAFT Polymerization of Vinyl Acetate
Monomer
(M)
RAFT
Agent
(M102)
Initiatora
(M103)/
Conditions
10.86
11 (4.98)
7.24
7.24
Conv
%
Mnb
Mn
(calc)c
PDI
AIBN (61)
60 C 16 h
96
22,700
18,000
1.24
11 (5.06)
ACHN (28)
75 C 16 h
93
13,400
11,440
1.29
11 (10.06)
ACHN (28)
75 C 16 h
95
7,100
5,880
1.25
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 polymerization. However, selection of the appropriate RAFT agent for the
monomers in tandem with the proper reaction conditions is crucial for
successful polymerization.
References
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
AIBN: 2,2-azobis(isobutyronitrile) (Aldrich Prod. No. 441090); ACHN: 1,1-azobis(cyclohexanecarbonitrile) (Aldrich Prod. No. 380210)
number average molecular weight in polystyrene equivalents.
c
calculated molecular weight based on complete consumption of RAFT agent.
(10)
(11)
O
S
S
CN
CN
11
12
(12)
(13)
(14)
(15)
(16)
(17)
(18)
O
S
(19)
S
CN
(20)
13
14
Moad, G.; Rizzardo, E.; Thang, S. H. Aust. J. Chem. 2005, 58, 379.
Moad, G.; Rizzardo, E.; Thang, S. H. Polymer 2008, 49, 1079.
Moad, G.; Rizzardo, E.; Thang, S. H. Acc. Chem. Res. 2008, 41, 1133.
Moad, G.; Chiefari, J.; Krstina, J.; Postma, A.; Mayadunne, R. T. A.; Rizzardo, E.;
Thang, S. H. Polym. Int. 2000, 49, 993.
Rizzardo, E.; Chiefari, J.; Mayadunne, R. T. A.; Moad, G.; Thang, S. H. ACS Symp. Ser.
2000, 768, 278.
Benaglia, M.; Chen, M.; Chong, Y. K.; Moad, G.; Rizzardo, E.; Thang, S. H.
Benaglia, M.; Chiefari, J.; Chong, Y. K.; Moad, G.; Rizzardo, E.; Thang, S. H. J. Am. Chem.
Soc. 2009, 131, 6914.
Moad, G.; Chong, Y. K.; Rizzardo, E.; Postma, A.; Thang, S. H. Polymer 2005, 46, 8458.
Moad, G.; Mayadunne, R. T. A.; Rizzardo, E.; Skidmore, M.; Thang, S. Macromol. Symp.
2003, 192, 1.
Chong, Y. K.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 2007, 40, 4446.
Postma, A.; Davis, T. P.; Evans, R. A.; Li, G.; Moad, G.; OShea, M. Macromolecules 2006,
39, 5293.
Postma, A.; Davis, T. P.; Li, G.; Moad, G.; OShea, M. Macromolecules 2006, 39, 5307.
Postma, A.; Davis, T. P.; Moad, G.; OShea, M. S. Macromolecules 2005, 38, 5371.
Chong, B.; Moad, G.; Rizzardo, E.; Skidmore, M.; Thang, S. H. Aust. J. Chem. 2006, 59,
755.
Rizzardo, E.; Chen, M.; Chong, B.; Moad, G.; Skidmore, M.; Thang, S. H. Macromol.
Symp. 2007, 248, 104.
Chong, Y. K.; Moad, G.; Rizzardo, E.; Skidmore, M. A.; Thang, S. H. Macromolecules
2007, 40, 9262.
Thang, S. H.; Chong, Y. K.; Mayadunne, R. T. A.; Moad, G.; Rizzardo, E. Tetrahedron Lett.
1999, 40, 2435.
Chong, Y. K.; Krstina, J.; Le, T. P. T.; Moad, G.; Postma, A.; Rizzardo, E.; Thang, S. H.
A Micro Review of Reversible Addition/

The less active RAFT agents with Z = NR2 (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
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-blockpolyLAM polymers with narrowed molecular weight distributions.9 This
approach was demonstrated with the use of 4-pyridinyl-N-methyldithiocarbamate derivatives to prepare PMMA-block-PVAc and PMAblock-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
S
N
S R
S R
N
base
S
H+
S
N
S R
N
H
RAFT
controls
VAc, NVP, NVC
S R
N
H
RAFT
controls
MMA, MA, St
Scheme 2. RAFT Agent capable of polymerization of both LAMs and MAMs

controlled by pH.
21
RAFT
Concepts and Tools for RAFT Polymerization
Concepts and Tools for RAFT Polymerization
Adapted from contributions by researchers at CSIRO

The RAFT Process
Classes of RAFT Agents
RAFT or Reversible Addition/Fragmentation Chain Transfer is a form of

living radical polymerization. RAFT polymerization was discovered at
CSIRO in 1998.1 It soon became the focus of intensive research, since the
method allows synthetic tailoring of macromolecules with complex
architectures including block, graft, comb, and star structures with
controlled molecular weight.2 RAFT polymerization is applicable to a
very wide range of vinyl monomers under a variety of experimental
conditions, including the preparation of water-soluble materials.3
Solubility and reactivity of a RAFT agent depend on the R and Z groups;

as a result, different RAFT agents are more suitable for specific classes of
monomers. The main classes of RAFT agents are:
The RAFT process involves conventional free radical polymerization of a

substituted monomer in the presence of a suitable chain transfer agent
(RAFT agent or CTA). Commonly used RAFT agents include thiocarbonylthio compounds such as dithioesters,1 dithiocarbamates,4,5
trithiocarbonates,6 and xanthates,7 which mediate the polymerization via
a reversible chain-transfer process. Use of a proper RAFT agent allows
synthesis of polymers with a high degree of functionality and narrow
distribution of molecular weights also referred to as a low polydispersity
index (PDI) as shown in Figure 1.
RAFT
Polymerization
15,000
Monomers
10,000
Monomers
Z1
S
S
In
In
In
Very high transfer constants

Prone to hydrolysis
May cause polymerization retardation under high concentrations
B) Trithiocarbonates
D) Xanthates
MW
500
Monomers
20,000
Monomers
Controlled Living
Free Radical
Polymerization
Lower transfer constants

More effective with less activated monomers
Made more active by electron-withdrawing substituents
Free radical leaving group, R

(must be able to reinitiate polymerization)
S
R
Weak C-S bond
A) Dithiobenzoates
Suitable
RAFT Agent
Reactive C-S double bond
Z
Z-group controls the reactivity of the
C-S double bond; influences the rate
of radical addition and fragmentation
Figure 2. General structure of a RAFT agent, where the R and Z subtituents impact
reaction kinetics. The choice of the RAFT agent is critical to obtain polymers with low PDI
and controlled architecture.
Aldrich.com
Figure 3. Four classes of RAFT agents: A) Dithiobenzoates, B) Trithiocarbonates,

C) Dithiocarbamates, and D) Xanthates.
A RAFT CTA typically has a thiocarbonylthio group (S = C-S) with

substituents R and Z that impact the polymerization reaction kinetics
and therefore, the degree of structural control. Initiation of the
polymerization reaction is accomplished utilizing conventional thermal,
photochemical, or redox methods, and the success of the RAFT
polymerization experiment is dependent upon selecting the appropriate
RAFT reagent for a particular monomer and reaction medium. This
general concept is depicted in Figure 2.
22
Activity determined by substituents on N

Effective with electron-rich monomers
Inconsistent Chain Length
Well-defined
Polymer
Z2
Figure 1. General comparison of polymers made with traditional radical polymerization

against those made using RAFT process.
Lower PDI
Higher functionality
D)
C)
S
C) Dithiocarbamates
Monomer
Traditional
Radical
Polymerization
B)
S
High transfer constants

More hydrolytically stable (than dithiobenzoates)
Cause less retardation
Greater Chain Length Control
X
X
X
A)
RAFT
RAFT Agent to Monomer Compatibility Table
Table 1. RAFT agents suitability for various monomer types. (Adapted from CSIROs RAFT
agent Monomer Matching guide).
R1
O
R2
CH3
N
S
H
N
CH3
CH3
styrenes
acrylates
acrylamides
+++
+++
+++
++
++
+++
H
N
O
R
N
H
vinyl esters
vinyl amides
+++
+++
+++
+++
+++
+++
++
++
+++
+++
methacrylates methacrylamides
The following procedures describe polymerization of methyl methacrylate and vinyl

acetate homopolymers and a block copolymer as performed by researchers at CSIRO.
Introduction
RAFT (Reversible Addition/Fragmentation Chain Transfer) is a form of
living radical polymerization involving conventional free radical
polymerization of a substituted monomer in the presence of a suitable
chain transfer (RAFT) reagent. Use of the appropriate RAFT agent and
polymerization conditions allows for the synthesis of polymers with low
PDI and high functionality. For a further explanation of RAFT technology
and its advantages, please read the review by researchers at CSIRO on
page 19.
CN
723002
C12H25S
Typical Procedures for Polymerizing

via RAFT
Reagents
CN
723029
RAFT Agent (Aldrich Prod. No.)

2-Cyano-2-propyl benzodithioate (722987)
CN
722987
O
S
OH
CN
722995
C12H25S
S
S
4-Cyano-4-(phenylcarbonothioylthio) pentanoic acid (722995)
OH
O
2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (723010)

Cyanomethyl dodecyl trithiocarbonate (723029)
CN
Cyanomethyl methyl(phenyl) carbamodithioate (723002)

2-Cyano-2-propyl dodecyl trithiocarbonate (723037)
CN
723037
C12H25S
4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid
(723274)
Typical Procedures for Polymerizing via RAFT
The application of RAFT agents with common monomers used in

polymerizations is shown in Table 1. The plus and minus symbols
represent the degree of compatibility between monomer classes and a
RAFT agent. For example, Aldrich Prod No. 723037 (fifth item down in
Table 1) is very useful in polymerizing styrenes, methacrylates and
methacrylamides, shows moderate activity for acrylates and acrylamides
but cannot polymerize vinyl esters or vinyl amides. This table can be
used as a guide for selecting the most appropriate RAFT agent for your
needs.
+++
++
++
+++
+++
+++
+++
+++
723274
Storage/Stability
S
C12H25
OH
S
O
723010
+++ = Well-suited
++ = Moderately suited
+ = Variable results
= Poorly suited
Please see the fold out compatibility table at the end of the book for
more information.
RAFT agents are sold for research purposes only:
see Aldrich.com/raftlicense.
723274 Store the product at -20 C and keep tightly closed. The
product is light sensitive.
722995 and 723037 Store the products at 2-8 C and keep tightly
closed.
722987, 723002, 723010, and 723029 Store the products at 2-8 C
and keep tightly closed. The products are light sensitive.
Note: Please consult the Material Safety Data Sheet for information
regarding hazards and safe handling practices.
References
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.;
Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 1998, 31,
5559.
McCormick, C.L.; Lowe, A.B. Acc. Chem. Res. 2004, 37, 312.
Mayadunne, R.T.A.; Rizzardo, E.; Chiefari, J.; Chong, Y.K.; Moad, G.; Thang, S.H.;
Destarac. M.; Charmot. D.; Franck, X.; Zard, S. Z. Macromol. Rapid. Commun. 2000, 21,
1035.
Mayadunne, R. T. A.; Rizzardo, E.; Chiefari, J.; Kristina, J.; Moad, G.; Postma, A.;
Thang, S. H. Macromolecules 2000, 33, 243.
Francis, R.; Ajayaghosh, A. Macromolecules 2000, 33, 4699.
RAFT Polymerization Procedures

1) Methyl Methacrylate Polymerization: using methyl methacrylate
(MMA, Aldrich Prod. No. M55909) as the monomer, AIBN (Aldrich Prod.
No. 441090) as the initiator, and a RAFT agent (Aldrich Prod. Nos.
722987 or 723274).
Prepare stock solution of methyl methacrylate (15 mL, 0.14 mol) and
AIBN (20.1 mg, 0.122 mmol) in 5 mL of benzene.
Aliquot 2 mL samples of stock solution into ampules containing
Aldrich Prod. No. 722987 (12.3 mg, 0.056 mmol) or Aldrich Prod.
No. 723274 (22.5 mg, 0.056 mmol). Note: Other glassware suitable for
handling air sensitive reactions, such as a Schlenk reaction tube
(Aldrich Prod. No. Z515981), may be used as an alternative to a sealed
ampule.
De-gas contents of ampules by three repeated freeze-evacuate-thaw
cycles (0.05 mm Hg) and seal under vacuum.
Polymerize by placing sealed ampule in heated oil bath (60 C) for
15 hours.
23
RAFT
Characterization of Poly(methyl methacrylate)
Typical Procedures for Polymerizing via RAFT
Table 1. Characteristics of poly(methyl methacrylate) synthesized by RAFT polymerization

RAFT Agent
Polymerization
Time
Mn
PDI
% Conv.
(NMR)
722987
4 hours
8468
1.14
24.5
722987
15 hours
30032
1.07
93.6
723274
15 hours
25959
1.08
98.5
Written by researchers in the Polymer Center of Excellence at Aldrich Materials Science.

2) Vinyl Acetate Polymerization: using vinyl acetate (Aldrich Prod.

No. V1503) as the monomer, AIBN (Aldrich Prod. No. 441090) as the
initiator, and a RAFT agent (Aldrich Prod. No. 723002).
Prepare solution of vinyl acetate (2.0 mL, 23.23 mmol), AIBN (2.0 mg,
0.012 mmol), and Aldrich Prod. No. 723002 (26.64 mg, 0.12 mmol) in
an ampule. Note: Other glassware suitable for handling air sensitive
reactions, such as a Schlenk reaction tube (Aldrich Prod.
No. Z515981), may be used as an alternative to a sealed ampule.
De-gas contents of the ampule by three repeated freeze-evacuatethaw cycles (0.05 mm Hg) and seal under vacuum.
Polymerize by placing sealed ampule in heated oil bath (60 C) for
16 hours.
Researchers at CSIRO have tested select Aldrich RAFT agents in the
polymerization of vinyl acetate and analyzed the resulting polymer. The
data are presented in Table 2 and Figure 1.
Characterization of Poly(vinyl acetate)

Table 2. Characteristics of poly(vinyl acetate) synthesized by RAFT polymerization.
RAFT Agent
Polymerization
Time
Mn
PDI
% Conv.
(NMR)
723002
16 hours
16,400
1.25
91
Auto-scaled Chromatogram
Introduction to Switchable RAFT Agents

Reversible Addition/Fragmentation Chain Transfer (RAFT) polymerization
is a versatile controlled radical polymerization method.1-3 For example,
most vinyl monomers which are polymerizable by radical polymerization
can be polymerized via RAFT.4 However, due to reactivity differences, the
appropriate RAFT agent must be selected for a given monomer type in
order to obtain living polymerization characteristics. In general, RAFT
agents such as dithioesters2 and trithiocarbonates5 work well with
controlling the polymerization of more-activated monomers (MAMs),
such as styrene (Sty), methyl acrylate (MA), and methyl methacrylate
(MMA), meanwhile dithiocarbamates6,7 and xanthates8 must be used to
control the polymerization of less activated monomers (LAMs), such as
vinyl acetate (VAc), N-vinylpyrrolidone (NVP), and N-vinylcarbazole (NVC).
Improper pairing (e.g., dithiocarbamate RAFT agent with MMA
monomer) will inhibit or significantly limit the polymerization.5
Differences in the reactivity of vinyl monomers have historically limited
the ability to form block copolymers comprised of MAMs and LAMs
(poly(MAM)-block-poly(LAM)) with a narrow molecular weight distribution. In an effort to overcome this limitation, CSIRO scientists have
recently reported switchable (universal) RAFT agents.1 These specialty
RAFT agents are dithiocarbamates that are able to control the
polymerization of MAMs when the pyridyl nitrogen is protonated and
then readily control the polymerization of LAMs when deprotonated
(Scheme 1).
21196
6.00
Universal/Switchable RAFT Agents for

Well-defined Block Copolymers: Agent
Selection and Polymerization
4.00
S
N
2.00
S
S R
S R
RAFT
0.00
MV
-2.00
controls
VAc, NVP, NVC
-4.00
base
-6.00
H+
-8.00
-12.00
-14.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
Minutes
SampleName BC-special- 16; Vial 2; Injection 1; Channel 410; Date Aquired 14/04/2010 8:09:31 PM
GPC Results
Adjusted
RT
MN
MW
29.603
29.603
16389
20518
2.00
1.80
1.60
dwt/d(logM)
Mz
Mz+1
Polydispersity
Baseline
Start
Baseline
End
24519
28453
1.251896
27.050
34.100
Mz+1 = 28453
Mz = 24519
MP = 211.96 MW = 20518
2.20
MP
21196
1.40
1.20
100.00
80.00
60.00
1.00
40.00
0.80
0.60
20.00
0.40
0.20
0.00
0.00
4.80
4.60
4.40
4.20
4.00
3.80
3.60
Log MW
dwt/d(logM)
Cumulative (%)
Figure 1. GPC analysis of poly(vinyl acetate) polymerized for 16 hours using Aldrich Prod.
No. 723002 as a RAFT agent.
N
H
Aldrich.com
N
H
S R
RAFT
controls
MA, MMA,S
Scheme 1. Differences in the canonical forms of protonated and deprotonated N-methyl,

N-(4-pyridyl)dithiocarbamates. When protonated the agents can control polymerization
of MAMs (such as Sty, MA, MMA) and then when deprotonated, the RAFT agents can
effectively control polymerization of LAMs (such as VAc, NVP and NVC).1,9
The synthesis of poly(MAM)-block-poly(LAM) can be performed in situ via

direct solution polymerization and is rapid and reversible. The highest
level of control over the polymerization is achieved by protonation of
the 4-pyridyl group with a stoichiometric amount of a strong organic
acid (e.g., p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc).10
Alternatively, coordination of the 4-pyridyl group with Lewis acids such
as Al(OTf)3 will also work.10 Deprotonation can be performed in situ
using organic bases such as N,N-dimethylaminopyridine (DMAP),1 or can
be achieved by passing a polymer solution through a bed of crushed
sodium carbonate.
RAFT agents are sold for research purposes only. For patent information,
24
S R
Practical Considerations
Cumulative (%)
Retention
Time
MN = 16389
-10.00
RAFT
A technical protocol describing the synthesis of poly(MAM)-block-poly

(LAM) via switchable RAFT agents is included on page 25.
Switchable RAFT Agent to Monomer

Compatibility Table
The compatibility of switchable RAFT agents with common monomers is
shown in Table 1. The check and dash symbols represent the
compatibility and incompatibility, respectively, between monomer
classes and a protonated and neutral form of switchable RAFT agent. For
example, 2-Cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate, Aldrich Prod No. 736236, is very useful in polymerizing styrenes,
methacrylates and methacrylamides when protonated, but shows poor
activity in controlling vinyl esters or vinyl amides.
N
R'
O
R'
O
R'
Styrenes
Acrylates
Methacrylates
Vinyl esters/amides
S
N
The following procedure describes polymerizations as performed by

researchers at CSIRO and researchers in the Polymer Center of Excellence
at Aldrich Materials Science.1
Product Description
RAFT (Reversible Addition/Fragmentation Chain Transfer) is a form of
living radical polymerization involving conventional free radical
polymerization of a monomer in the presence of a suitable chain transfer
(RAFT) reagent. RAFT technology can be used with a wide range of
monomers by all modes of free radical polymerization (solution,
emulsion, and suspension). The appropriate RAFT agent must be
selected for the monomer of interest. Historically there have been
no "universal" RAFT agents capable of preparing block copolymers
comprised of both lower activity monomers (LAMs; e.g., N-vinylpyrrolidone (Aldrich Prod. No. V3409), vinyl acetate (Aldrich Prod.
No. V1503), etc.), along with more active monomers (MAMs; e.g.,
acrylates, methacrylates, styrenes, etc.). However, with the development
of a new class of stimuli responsive, "pH-switchable/Universal" RAFT
agents, the synthesis of poly(MAM)-block-poly(LAM) can be performed
in situ via direct solution polymerization, and is rapid and reversible. The
highest level of control over the polymerization is achieved by
protonation of the 4-pyridyl group with a stoichiometric amount of a
strong organic acid (e.g., p-toluenesulfonic acid, trifluoromethanesulfonic
acid, etc).2 Alternatively, coordination of the 4-pyridyl group with Lewis
acids such as Al(OTf)3 will also work.2 Deprotonation can be performed
in situ using organic bases such as N,N-dimethylaminopyridine (DMAP),1
or can be achieved by passing a polymer solution through a bed of
crushed sodium carbonate. For a further explanation of RAFT technology
and its advantages, please read the review by researchers at CSIRO on
page 19.
Reagents
Switchable RAFT Agent (Aldrich Prod. No.)
Methyl 2-propionate methyl(4-pyridinyl)carbamodithioate (735639)
2-Cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate (736236)
S-cyanomethyl-N-methyl-N-(pyridin-4-yl)carbamodithioate (738689)
S
N
Polymerization Procedure with

Universal/Switchable RAFT Agents
Polymerization Procedure with Universal/Switchable RAFT Agents
In order to prepare well-defined block copolymers using switchable

RAFT agents, the MAM block segment should be polymerized first with a
protonated RAFT agent, followed by deprotonation and subsequent
polymerization of the LAM block(s).1,9,10 This is primarily due to the fact
that terminal LAM groups are poor radical leaving groups, leading to
poor blocking efficiency in the presence of MAMs, whereas poly(MAM)s
tend to have high chain transfer constants relative to LAMs. In certain
cases, it is strongly recommended (particularly when initiating the
polymerization of a vinyl acetate block from a polystyrene macro chain
transfer agent) that all traces of residual MAM are removed (either by
precipitation or vacuum distillation). Trace MAM in the reaction solution
could lead to inhibition of future polymerization events. Additionally, in
some cases addition of an intermediate monomer may be required in
order to bridge the reactivity between MAM and LAM units. In the case
of styrene and vinyl acetate, a small amount of methyl acrylate (~5%) can
be added, after all Sty monomer is consumed or removed, to a solution
of the polystyrene macroCTA and vinyl acetate. The polystyrene
macroCTA will incorporate the methyl acrylate and the vinyl acetate in a
gradient fashion before leading to a true vinyl acetate block once all
methyl acrylate is consumed.
N
H
N,N-Dimethyl N,N-di(4-pyridinyl)thiuram disulfide (735973)
Storage/Stability
Table 1. The neutral and protonated switchable RAFT agents with their suitability for
selected monomer types ( = compatible; = incompatible).
The products are light sensitive. Store the products at 2-8 C and keep
tightly closed.
References
(1)
Benaglia, M.; Chiefari, J.; Chong, Y.K.; Moad, G.; Rizzardo, E.; Thang, S.H. J. Am. Chem.
Soc. 2009, 131, 6914.
Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A. ;
Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 1998, 31,
5559.
(3) Moad, G.; Rizzardo, E.; Thang, S. H. Aust. J. Chem. 2005, 58, 379.
(4) McCormick, C.L.; Lowe, A.B. Acc. Chem. Res. 2004, 37, 312.
(5) Mayadunne, R. T. A.; Rizzardo, E.; Chiefari, J.; Kristina, J.; Moad, G.; Postma, A.;
Thang, S. H. Macromolecules 2000, 33, 243.
(6) Mayadunne, R.T.A.; Rizzardo, E.; Chiefari, J.; Chong, Y.K.; Moad, G.; Thang, S.H.;
(7) Destarac. M.; Charmot. D.; Franck, X.; Zard, S. Z. Macromol. Rapid. Commun. 2000, 21,
1035.
(8) Francis, R.; Ajayaghosh, A. Macromolecules 2000, 33, 4699.
(9) Moad, G.; Rizzardo, E.; Thang, S.H. Material Matters 2010, 5, 2.
(10) Keddie, D.J.; Guerrero-Sanchez, C.; Moad, G.; Rizzardo, E.; Thang, S.H. Macromolecules,
2011, 44 , 6738.
(2)
25
RAFT
Switchable RAFT Polymerization Procedures
Example procedures of RAFT polymerization utilizing "Switchable"
RAFT reagents (as performed by researchers at CSIRO):
Polymerization Procedure with Universal/Switchable RAFT Agents
1) Poly(methyl methacrylate) homopolymer

2) Poly(vinyl acetate) homopolymer
3) Poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer
1) Methyl Methacrylate Polymerization: using methyl methacrylate
(MMA, Aldrich Prod. No. M55909) as the monomer, 2,2-Azobis
(2-methylpropionitrile) (AIBN) (Aldrich Prod. No. 441090) as the initiator,
and a Switchable RAFT agent 2-Cyanopropan-2-yl N-methyl-N-(pyridin4-yl)carbamodithioate (Aldrich Prod. No. 736236).
A stock solution (A) of trifluoromethanesulfonic acid (100 L or
170 mg, Aldrich Prod. No. 347817) in acetonitrile (5.0 mL) was
prepared.
A second stock solution (B) was prepared containing methyl
methacrylate (7.0 mL), AIBN (10 mg), 2-Cyanopropan-2-yl N-methylN-(pyridin-4-yl)carbamodithioate (50.02 mg), acetonitrile (2.0 mL) and
stock solution A (1.0 mL) from previous step.
2.0 mL of stock solution B was transferred to an ampule, degassed by
three repeated freeze-evacuate-thaw cycles and sealed. Other
glassware suitable for handling air sensitive reactions, such as a
Schlenk reaction tube, may be used as an alternative to a sealed
ampule.
The ampule was polymerized at 60 C for 16 hours. Characterization
data for this polymerization is presented in Table 1.
To remove color from the final product the polymer was dissolved in
excess dichloromethane and passed through a crushed sodium
carbonate bed. A color change from yellow to colorless occurs.
Table 1. Characteristics of PMMA synthesized by switchable RAFT polymerization using
Aldrich Prod. No. 736236.
Reaction Time
Mn
PDI
% Conv.
3 hours
15,500
1.56
27.6%
6 hours
19,200
1.58
51.1%
16 hours
33,050
1.25
98.0%
3) Poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer:

was prepared by essentially combining the previous two procedures.
The PMMA polymer from the PMMA polymerization procedure is now
the macro chain transfer agent (macroCTA) for controlling the second
vinyl acetate block. The last step of the PMMA polymerization was
passing the polymer over a crushed bed of sodium carbonate, which
deprotonated the RAFT functionality and prepared the macroCTA for
polymerization of vinyl acetate.
PMMA-block-PVac was prepared by using vinyl acetate (Aldrich Prod.
No. V1503) as the monomer, ACHN (Aldrich Prod. No. 380210) as the
initiator, and the PMMA macro chain transfer agent (macroCTA)
prepared in the previous Procedure 1 (PMMA, 33,050 Da, PDI = 1.25). The
poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer was
synthesized under reaction conditions similar to Procedure 2.
A solution of ACHN (10.3 mg), vinyl acetate (10 mL) and ethyl acetate
(5.0 mL) was prepared. An aliquot (3.0 mL) of this stock solution was
transferred into an ampule containing the macroCTA, the mass of
which depends on the molecular weight obtained. This was degassed
by three repeated freeze, pump, thaw cycles and sealed.
The ampule was heated at 75 C for 3 days. After the reaction, the unreacted monomer was removed with a rotary evaporator. The resulting
poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer
displayed a low polydispersity as shown in Table 3.
Table 3. Characteristics of poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer
synthesized by switchable RAFT technology.
Reaction Time
Mn
PDI
% Conv.
3 days
55,900
1.39
80%
The Switchable RAFT agents are able to successfully polymerize

monomers of different reactivity and achieve narrow molecular weight
distributions as shown in Figure 1.
2) Vinyl Acetate Polymerization: using vinyl acetate (Aldrich Prod.

No. V1503) as the monomer, 1,1-Azobis(cyclohexanecarbonitrile)
(ACHN) (Aldrich Prod. No. 380210) as the initiator, S-cyanomethyl Nmethyl,N-(pyridin-3-yl) carbamodithioate (Aldrich Prod. No. 738689) as
the Switchable RAFT agent, and ethyl acetate as solvent (Aldrich Prod.
No. 270989).
A solution of ACHN (10.3 mg), vinyl acetate (10 mL) and ethyl acetate
(5.0 mL) was prepared. An aliquot (3.0 mL) of this stock solution was
transferred into an ampule containing S-cyanomethyl N-methyl,N(pyridin-3-yl) carbamodithioate (35.0 mg), which was degassed by
three repeated freeze-evacuate-thaw cycles and sealed.
The ampule was heated at 75 C for 3 days. After the reaction, the unreacted monomer was removed on rotary evaporator. The resulting
poly(vinyl acetate) displayed a low polydispersity as shown in Table 2.
Table 2. Characteristics of poly(vinyl acetate) synthesized by switchable RAFT
polymerization using Aldrich Prod. No. 738689.
Reaction Time
Mn
PDI
% Conv.
3 days
8,900
1.24
54.8%
24
28
32
36
Elution Time (min)
40
Figure 1. GPC analysis of poly(methyl methacrylate)-block-poly(vinyl acetate)

polymerized for 16 hours using PMMA as a macroCTA.1 Reprinted with permission from
the American Chemical Society.
Gel permeation chromatography (GPC) method: Waters Associates liquid

chromatograph equipped with differential refractometer and 3mixed C
and 1 mixed E PLgel column. Tetrahydrofuran (flow rate of 1.0 mL/min)
was used as eluent at 22 2 C. The columns were calibrated with
narrow polydispersity polystyrene standards. The molecular weights are
reported as polystyrene equivalents.
References
(1)
(2)
26
Aldrich.com
Benaglia, M.; Chiefari, J.; Chong, Y.K.; Moad, G.; Rizzardo, E.; Thang, S.H. J. Am. Chem.
Soc. 2009, 131, 6914.
Keddie, D.J.; Guerrero-Sanchez, C.; Moad, G.; Rizzardo, E.; Thang, S.H. Macromolecules,
2011, 44 , 6738.
RAFT
RAFT Agents
For a complete list of available RAFT agents, visit Aldrich.com/raftagent.
Name
Structure
4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic
acid
2-Cyano-2-propyl dodecyl trithiocarbonate
S H3C CN
CH3(CH2)10CH2
S H3C CN
CH3(CH2)10CH2
Poly(ethylene glycol) methyl

ether (4-cyano-4-pentanoate
dodecyl trithiocarbonate), average Mn 2,400
CH3
S H3C CN
OH
CH3(CH2)10CH2S

O
S
CH3(CH2)10CH2S
OCH3
S H3C CN
O
CH3(CH2)10CH2S
S H3C CN
OCH3
n
O
CH3(CH2)10CH2S
S H3C CN
OCH3
n
O
CH3(CH2)10CH2S
S H3C CN
2-Phenyl-2-propyl benzodithioate
S H3C CH
1-(Methoxycarbonyl)ethyl benzodithioate
CH3
OCH3
S
O
2-Cyano-2-propyl 4-cyanobenzodithioate
OCH3
S H3C C N
S
CH3
Prod. No.
723274-1G
723274-5G
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
760110-1G
RAFT agent for controlled radical polymerization; This
760110-5G
alcohol-functionalized RAFT CTA would allow wide
variety of pre- and post-polymerization functionalization;
including standard coupling reactions and even ringopening polymerization; allowing for poly(vinyl)-blockpoly(ROP) polymers (e.g. Polystyrene-block-poly(L-lactide);
etc). This is best suited for methacrylate/methacrylamide/
styrenic monomers.
RAFT Agents
4-Cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol

ether 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, average Mn 10,400
OH
Description
RAFT agent for controlled radical polymerization; especially suited for the polymerization of methacrylate,
methacrylamide and styrene monomers. Chain Transfer
Agent (CTA)
RAFT agent for controlled radical polymerization; espe- 753033-1G

cially suited for the polymerization of styrene, acrylate
and acrylamide monomers to make lithographically and
biologically important PEG-block copolymers. Chain
Transfer Agent (CTA)
751626-1G
cially suited for the polymerization of styrene; acrylate
751634-1G
752487-1G
RAFT agent for controlled radical polymerization; especially suited for the polymerization of methacrylates/
methacrylamides, and to a lesser extent acrylates/
acrylamides and styrenes; Chain Transfer Agent (CTA)
731269-1G
731269-5G
RAFT agent for controlled radical polymerization; wellsuited for polymerization of methacrylates, methacrylamides, and to a lesser extent styrenes, acrylates, and
acrylamides. Chain Transfer Agent (CTA)
751138-1G
RAFT agent for controlled radical polymerization; especially suited for the polymerization of methyl methacrylate and styrene monomers. Chain Transfer Agent (CTA)
731277-1G
731277-5G
RAFT agent for controlled radical polymerization; especially suited for the polymerization of methacrylate and
methacrylamide monomers. Chain Transfer Agent (CTA)
722995-1G
722995-5G
RAFT agent for controlled radical polymerization; especially suited for the polymerization of methacrylate and
methacrylamide monomers. Chain Transfer Agent (CTA)
722987-1G
722987-5G
RAFT agent for controlled radical polymerization; Chain

Transfer Agent (CTA) well-suited for methacrylates,
methacrylamides, and styrenes.
760439-1G
760439-5G
N C
4-Cyano-4-(phenylcarbonothioylthio)pentanoic acid
S H3C CN
OH
S
O
2-Cyano-2-propyl benzodithioate
S H3C CN
Benzyl benzodithioate
CH3
27
RAFT
Name
Structure
Ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate
S H3C CH3
O
S
O
CH3
Methyl 2-phenyl-2-(phenylcarbonothioylthio)acetate
OCH3
RAFT Agents
4-Cyano-4-(phenylcarbonothioylthio)pentanoic acid Nsuccinimidyl ester
S H3C CN
O
O
O
Ethyl 2-(phenylcarbonothioylthio)propionate
CH3
O
CH3
2-(Dodecylthiocarbonothioylthio)propionic acid
O
S
CH3(CH2)10CH2S
S
2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid
OH
CH3
S H3C CH3
CH3(CH2)10CH2
OH
S
O
Methyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate
O
CH3(CH2)10CH2S
OCH3
S H3C CH3
2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid Nhydroxysuccinimide ester

ether (2-methyl-2-propionic
acid dodecyl trithiocarbonate),
average Mn 10,400
Poly(ethylene glycol) bis[2-(dodecylthiocarbonothioylthio)-2methylpropionate], average Mn
10,800
2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid 3azido-1-propanol ester
2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid pentafluorophenyl ester
CH3(CH2)10CH2S
O
S H3C CH3
O
S
N
O
O
O
S
CH3(CH2)10CH2S
O
S
CH3(CH2)10CH2S
S H3C CH3
CH3(CH2)10CH2S
F
F
F
OCH3
n
S H3C CH3
Prod. No.
741701-1G
RAFT agent for controlled radical polymerization; Chain 761257-1G

761257-5G
Transfer Agent (CTA) well-suited for polymerization of
methacrylates and methacrylamides.
Reversible Addition Fragmentation Chain Transfer (RAFT)
Polymerization
S
S
Description
RAFT agent for controlled radical polymerization; wellsuited for polymerization of methacrylates, methacrylamides, and to a lesser extent styrenes, acrylates, and
acrylamides. Chain Transfer Agent (CTA)
H3C CH3 S
O
S
SCH2(CH2)10CH3
O
S H3C CH3
O
S
O
N3
H3C CH3 S
O
S
SCH2(CH2)CH3
O
F
RAFT agent for controlled radical polymerization; This is

the NHS protected version of 722995; well suited for
methacrylates and methacrylamides; Chain Transfer
Agent (CTA)
758353-1G
RAFT agent for controlled radical polymerization; especially suited for methacrylates and methacrylamides;
Chain Transfer Agent (CTA)
760455-1G
RAFT agent for controlled radical polymerization; especially suited for the polymerization of styrene, acrylate
and acrylamide monomers. Chain Transfer Agent (CTA)
749133-1G
749133-5G
723010-1G
723010-5G
RAFT agent for controlled radical polymerization; especially suited for the polymerization of styrene; acrylate
and acrylamide monomers. Chain Transfrer Agent (CTA)
740497-1G
740497-5G
Functionalized RAFT agent for controlled radical polymerization; especially suited for the polymerization of
styrene; acrylate and acrylamide monomers. NHS ester
terminus can be used to conjugate to a variety of
biomolecules. Chain Transfer Agent (CTA).
741035-1G
741035-5G

cially suited for the polymerization of styrene; acrylate;
cially suited for the polymerization of styrene; acrylate;
741698-1G
Functionalized RAFT agent for controlled radical poly741698-5G
merization; especially suited for the polymerization of
styrene, acrylate and acrylamide monomers. Azide group
can be used to conjugate to a variety of alkynefunctionalized biomolecules. Chain Transfer Agent (CTA).
RAFT agent for controlled radical polymerization; especially suited for the polymerization of styrene; acrylate
740810-1G
740810-5G
28

ether 2-(dodecylthiocarbonothioylthio)-2-methylpropionate,
average Mn 1,100

Mn 5,000

Mn 2,000
Aldrich.com
C12H25

C12H25

cially suited for the polymerization of styrene, acrylate,
C12H25

cially suited for the polymerization of styrene, acrylate,
O
O
CH3 CH3 S
O
O
CH3 CH3 S
O
O
S
n
CH3 CH3 S
RAFT
Name
Structure
Cyanomethyl dodecyl trithiocarbonate

Poly(ethylene glycol) bis[2-(dodecylthiocarbonothioylthio)-2methylpropionate], average Mn
5,700
S
CH3(CH2)10CH2
O
S
CH3(CH2)10CH2S
H3C CH3 S
O
S
SCH2(CH2)10CH3
n
O
S H3C CH3
Cyanomethyl methyl(phenyl)
carbamodithioate
CN
CH3
N
S
CN
S
S
N
Benzyl 1H-pyrrole-1-carbodithioate
CN
RAFT agent for controlled radical polymerization; wellsuited for polymerization of styrenes, acrylates, and
acrylamides (MAMs) to generate a triblock copolymer
with a PEG block in the center.
741728-1G

cially suited for the polymerization of vinyl ester and vinyl 723002-5G
amide monomers. Chain Transfer Agent (CTA)
RAFT agent for controlled radical polymerization; wellsuited for vinyl acetates and vinyl benzoates. Chain
751200-1G
751200-5G
753106-5G
RAFT agent for controlled radical polymerization; wellsuited for polymerization of vinyl esters and vinyl amides 753106-1G
(LAMs)
N
S
Prod. No.
723029-1G
723029-5G
Bis(thiobenzoyl) disulfide
Precursor for the synthesis of RAFT agents for controlled 723118-5G

radical polymerization.
S
S
Cyanomethyl diphenylcarbamodithioate
Description
Bis(dodecylsulfanylthiocarbonyl)
disulfide
S
CH3(CH2)10CH2
CH2(CH2)10CH3
Precursor for the synthesis of RAFT agents for controlled 723126-5G

radical polymerization.

Name
1-Succinimidyl-4-cyano-4[N-methyl-N-(4-pyridyl)carbamothioylthio]pentanoate
Structure
Description
O
S H3C CN
H3C
O
O
N
2-Cyanopropan-2-yl Nmethyl-N-(pyridin-4-yl)carbamodithioate
S H3C CN
H3C
CH3
CN
Cyanomethyl methyl(4pyridyl)carbamodithioate
S
H3C
Methyl 2-propionate
methyl(4-pyridinyl)carbamodithioate
S
H3C
CH3
OCH3
S
O
N,N-Dimethyl N,N-di(4pyridinyl)thiuram disulfide
S
H3C
S S
CH3
Prod. No.
Switchable RAFT agent for controlled radical polymer- 751227-1G

ization. The neutral form is well-suited for polymerization of vinyl esters and vinyl amides (LAMs), and the
protonated form is well-suited for styrenes acrylates and
methacrylates (MAMs). NHS ester can be used to
functionalize a wide variety of biomolecules. Chain
736236-5G
methacrylates (MAMs). Chain Transfer Agent (CTA)
738689-5G
735639-5G
Precursor for the synthesis of novel switchable RAFT
agents for controlled radical polymerization. Chain
735973-5G
29
RAFT
Radical Initiators
For a complete list of available radical initiators, visit Aldrich.com/crp.
Name
Structure
1,1-Azobis(cyclohexanecarbonitrile)
N
CN
Radical Initiators
2,2-Azobis(2-methylpropionamidine)
dihydrochloride
Prod. No.
380210-25G
380210-100G
97%
440914-25G
440914-100G
98%
441090-25G
441090-100G
98.0%, T
11590-25G
11590-100G
CN
NH
H3C CH3
H2N
N
N
NH2
H3C CH3
NH
2,2-Azobis(2-methylpropionitrile)
Purity
98%
2HCl
H3C CH3
N
C N
N
H3C CH3
N C
4,4-Azobis(4-cyanovaleric acid)
H3C CN
HO
O
N
N
H3C CN
OH
Materials Science
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weight distributions are now available:
Polystyrene-block-poly(acrylic acid)
O
O
Polystyrene-block-poly(methyl methacrylate)
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N3
m
OH
PS-block-PAA
H
m
Diverse functionalities, including azides!

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30
Aldrich.com
O
O
PS-block-PMMA
NMP
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
Introduction
O O
+ O N
initiation
M
R
O
O N
thermally labile
alkoxyamine bond
R4
O N
R1
R5
R2 R3
general NMP
initiator structure
reversible
termination
O N
nitroxide-trapped alkoxyamine
structure, A
Block Copolymer Synthesis Using a Commercially Available

Nitroxide-mediated Radical Polymerization (NMP) Initiator
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.
propagation
O N
O
O N
reversible
termination
reversible termination events
provide controlled
polymerization
propagation
propagation to polymer
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.
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.1
Initially, nitroxides were employed as additives to reversibly terminate
polymer chains initiated by a separate radical source.2 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.3 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 NMP will experience a renewed vigor of investigation. With our
31
NMP
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
Aldrich Prod.
No. 710733
O
O
capping the propagating chain ends during polymerization), to prepare

an amphiphilic diblock copolymer precursor, poly(tert-butyl acrylate)-bpoly(4-acetoxystyrene) with a controlled molecular weight and a narrow
molecular weight distribution (Scheme 2).4
II
O
O
N
140
tert-Butyl acrylate
Aldrich Prod.
No. 327182
"Universal initiator"
Aldrich Prod.
No. 700703
4-Acetoxystyrene
Aldrich Prod.
No. 380547
125 C, 36 h
50% conv.
80% yield
O
N
50
140
125 C, 4 h
25% conv.
87% yield
MnGPC = 18.220 Da
MnNMR = 19.130 Da
PDI = 1.10
MnGPC = 26.330 Da
MnNMR = 26.620 Da
PDI = 1.12
Synthesis of poly(t-butyl acrylate)140 (I)

H NMR and 13C 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 N2 atmosphere, at room temperature, was added
(124 mg, 0.381 mmol, Aldrich Prod No. 700703), 2,2,5-trimethyl-4phenyl-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 freezepump-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), 1H 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 H2O/MeOH (v:v, 1:4) three times to afford PtBA as a
white powder, (4.1 g, 80% yield based upon monomer conversion);
MnNMR = 19,130 g/mol, MnGPC = 18,220 g/mol, PDI = 1.10. 1H NMR
(CD2Cl2, ppm): 1.43 (br, 1290 H), 1.80 (br, 70 H), 2.21 (br, 160 H),
7.14-7.26 (m, 10 H). 13C NMR (CD2Cl2, ppm): 28.4, 36.5, 38.0, 42.5, 80.9,
174.4. The GPC data can be seen in Figure 2.
GPC trace of I
100
80
60
40
20
0
16
18
20
22
24
Time (min)
26
Figure 2. Molecular weight distribution of I. Mn = 18,220 g/mol, PDI = 1.10
1H NMR spectrum of I
Kinetic plot of I
50
Conversion (percent)
120
RI Response (mW)

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.
0 PPM
Figure 3. H NMR spectrum of I
40
30
13
C NMR spectrum of I
20
10
0
y = 1.9876 + 1.3179x R= 0.99643
10
15 20 25 30
Time (hours)
35 40
200
Figure 4.
150
13
C NMR spectrum of I
Figure 1. Percent conversion of monomers vs. time
32
Aldrich.com
100
50
0 PPM
NMP
Synthesis of poly(t-butyl acrylate)140-b
-poly(acetoxystyrene)50 (II)
Conversion (percent)
24
20
16
0 PPM
Figure 7. H NMR spectrum of II
13
C NMR spectrum of II
200
Figure 8.
13
150
100
50
0 PPM
C NMR spectrum of II
120
100
Normalized GPC Traces

PtBA
PtBA-b-PAS
80
60
40
20
12
0
16
18
20
22
24
26
Time (min)
Figure 9. Normalized GPC traces showing molecular weight distributions of

polymers I and II.
y = -0.178 + 6.498x R= 0.99874
0
0
Time (hours)
Conclusions
Figure 5. Percent conversion of monomers vs. time
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 nor technique, beyond those employed
for standard radical polymerizations, but only synthesis of the
corresponding 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
supramolecularly 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.
GPC trace of II
160
RI Response (mW)
RI Response (mW)
Kinetic plot of II
28
120
80
40
0
16
18
20
22
24

H NMR and 13C 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 N2 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 freezepump-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), 1H 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
H2O / 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); MnNMR =
26,620 g/mol, MnGPC = 26,330 g/mol, PDI = 1.12. 1H 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). 13C 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.
H NMR spectrum of II
26
Time (min)
Figure 6. Molecular weight distribution of II. Mn = 26,330 g/mol, PDI = 1.12
33
NMP
References
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.
(1)
(2)
(3)
(4)
Hawker, C. J. J. Am. Chem. Soc. 1994, 116, 11185.

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.
Benoit, D.; Chaplinski, V.; Braslau, R.; Hawker, C. J. J. Am. Chem. Soc. 1999, 121, 3904.
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, visit Aldrich.com/crp.
Name
Structure

N-tert-Butyl-N-(2-methyl-1phenylpropyl)-O-(1-phenylethyl)hydroxylamine
N-tert-Butyl-O-[1-[4-(chloromethyl)phenyl]ethyl]-N(2-methyl-1-phenylpropyl)
hydroxylamine
Description
Prod. No.
CH3 t-Bu CH3

N
H3 C
O
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
CH3 t-Bu CH3

N
O
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
Stable nitroxide radical useful in controlling living

radical polymerizations
710733-250MG
710733-1G

polymerizations
426369-1G
426369-5G

radical polymerizations, with a methacrylate functionality for cross-linking or orthogonal polymerization.
730297-1G
H3C
Cl
2,2,5-Trimethyl-4-phenyl3-azahexane-3-nitroxide
H 3C
CH3 O CH3
N
CH3
CH3
TEMPO
H3C
H3C
CH3
CH3
N
O
TEMPO methacrylate
O
O
CH2
CH3
H3C
H3C
CH3
N
O
CH3
Materials Science
Material Matters
TM
TM
Materials Science
Materials Science
Volume 6, Number 3
Volume 5, Number 1 2010
A Quarterly Periodical from Aldrich Materials Science
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Theme-based technical reviews by leading experts
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Reversible Addition Fragmentation

Chain Transfer (RAFT) Polymerization
Start living with controlled polymerization
Aldrich.com
Block Copolymer Synthesis Using a

Commercially Available NitroxideMediated 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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Polymers for Sutures, Medical
Devices, Drug Delivery Systems
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Supporting Your Drive to Future Technologies
Degradable Poly(ethylene
glycol) Hydrogels for 2D and
3D Cell Culture
Polyelectrolyte Multilayer
Films and Membrane
Functionalizaton
The Use of Block Copolymers
in Nanoscale Patterning
Have you seen these recent issues? If not, get your

complimentary subscription today: Aldrich.com/mm
sigma-aldrich.com
34
Polymers for Advanced Architectures
Modern Polymerization Techniques
Monomer Index
Styrene Monomers
For a complete list of available styrene, functionalized styrene, and substituted styrene monomers, visit Aldrich.com/monomers.
Functionalized Styrene Monomers

Name
Structure
4-Vinylbenzocyclobutene
4-[N-(Methylaminoethyl)
aminomethyl]styrene
H2C
H3C
CH2
H
N
N
H
4-Benzhydrylstyrene
Purity
Additive
Prod. No.
97%
733377-1G
>90%
725609-1G
96%
725595-1G
97%
708127-1G
708127-5G
708127-25G
97%
KOH as inhibitor
560839-1G
560839-5G
90%
292273-5G
292273-25G
97%
3,5-di-tert-butylcatechol 0.1% as inhibitor
132683-1G
132683-5G
97%
132675-5G
98%
124141-10G
124141-25G
97%
hydroquinone 0.1% as stabilizer
160679-5G
160679-25G
98%
3,5-di-tert-butylcatechol 0.1% as stabilizer
C71009-1G
97%
4-tert-butylcatechol 500 ppm as inhibitor
C71203-10G
C71203-50G
98%
tert-butylcatechol 100 ppm as stabilizer
C57200-25G
99%
D74509-2.5G
D74509-10G
90%
tert-butylcatechol 500 ppm as inhibitor
436887-25ML
436887-100ML
97%
tert-butylcatechol 50-100 ppm as inhibitor

nitromethane 700-1100 ppm as inhibitor
338729-25G
338729-100G
CH2
4-(Diphenylphosphino)
styrene
P
CH2
3-Vinylaniline
NH2
CH2
Br
CH2
2-Bromostyrene
CH2
Br
3-Bromostyrene
Br
CH2
4-Bromostyrene
CH2
Styrene Monomers
-Bromostyrene
Br
2-Chlorostyrene
CH2
Cl
3-Chlorostyrene
CH2
Cl
4-Chlorostyrene
CH2
Cl
4-Chloro--methylstyrene
CH3
CH2
Cl
2,6-Dichlorostyrene
Cl
CH2
Cl
4-Vinylbenzyl chloride
Cl
H2C
Vinylbenzyl chloride
Cl
H 2C
Cl
H2 C
35
Monomer Index
Name
Structure
2-Isopropenylaniline
NH2
Purity
Additive
Prod. No.
98%
194212-5G
194212-25G
97%
KOH as inhibitor
560839-1G
560839-5G
97%
536180-1G
536180-5G
97%
476382-1G
476382-10G
96%
523089-5G
97%
254738-1G
254738-5G
95%
BHT 200 ppm as inhibitor
361771-250ML
361771-1L
CH2
CH3
3-Vinylaniline
NH2
CH2
4-Vinylaniline
NH2
H2C
N,N-Dimethylvinyl-benzylamine, mixture of isomers
H3C
CH3
N
CH2
3-Vinylbenzoic acid
O
OH
CH2
4-Vinylbenzoic acid
O
OH
H2C
3-Isopropenyl-,dimethylbenzyl
isocyanate
H3C CH3
NCO
CH2
Styrene Monomers
H3C
Substituted Styrene Monomers

Name
Structure
-Methylstyrene
CH3
Purity
Additive
Prod. No.
99%
p-tert-butylcatechol 15 ppm as inhibitor
M80903-5ML
M80903-100ML
M80903-1L
99%
522864-250ML
522864-1L
99%
184675-5G
96%
3,5-di-tert-butylcatechol as inhibitor
M80806-10ML
M80806-100ML
M80806-500ML
97%
255173-250ML
255173-1L
97%
262633-5G
98%
tert-Butylcatechol 500 ppm as stabilizer
361135-5G
95%
tert-butylcatechol <0.05% as inhibitor
259780-5G
93%
523933-250ML
523933-1L
CH2
Methylstyrene
CH2
CH3
3-Methylstyrene
CH2
CH3
4-Methylstyrene
CH2
H3C
1,3-Diisopropenylbenzene
CH3
CH2
H3C
CH2
2,4-Dimethylstyrene
CH2
H3C
2,5-Dimethylstyrene
CH3
H3C
CH2
CH3
2,4,6-Trimethylstyrene
CH3
CH2
H3C
4-tert-Butylstyrene
H3 C
H3 C
CH3
36
Aldrich.com
CH3
CH2
Monomer Index
Name
Structure
4-Vinylanisole
OCH3
Purity
Additive
Prod. No.
97%
141003-5G
141003-25G
96%
monomethyl ether hydroquinone 200-300

ppm as inhibitor
380547-5ML
380547-25ML
99%
455644-50ML
technical grade
hydroquinone 1% as inhibitor
154466-5G
154466-10G
98%
4-tert-butylcatechol as inhibitor
290505-5G
>99%
219452-1G
99%
tert-butylcatechol as inhibitor
155799-1G
155799-10G
99%
4-tert-butylcatechol 0.1% as inhibitor
369594-1G
99%
4-tert-butylcatechol as inhibitor
366692-1G
98%
369608-1G
99%
374407-250MG
374407-1G
99%
p-tert-butylcatechol 0.1% as inhibitor
196916-25G
96%
N26601-2.5G
N26601-10G
99%
458694-100G
458694-250G
98%, optical grade
453870-1G
95%
V2909-5G
V2909-25G
V1805-1G
V1805-10G
97%
V1708-1G
V1708-5G
H2C
4-Acetoxystyrene
CH2
H3C
H3C
CH3
O
CH3
4-tert-Butoxystyrene
CH2
3,4-Dimethoxystyrene
CH2
H3CO
OCH3
2-Fluorostyrene
CH2
F
3-Fluorostyrene
CH2
F
4-Fluorostyrene
CH2
F
2-(Trifluoromethyl)styrene
CH2
CF3
CH2
CH2
F3C
2,6-Difluorostyrene
F
CH2
F
2,3,4,5,6-Pentafluorostyrene
F
F
Styrene Monomers
CF3
CH2
F
F
3-Nitrostyrene
CH2
NO2
(Vinylbenzyl)trimethylammonium chloride
Cl
H2C
2-Vinylnaphthalene
2-Vinylnaphthalene
CH3
N CH3
CH3
CH2
CH2
4-Vinylbiphenyl
9-Vinylanthracene
CH2
CH2
37
Monomer Index
Acrylate Monomers
For a complete list of available acrylate monomers, visit Aldrich.com/acrylic.
Monofunctional Acrylate Monomers

Name
Structure
2-Chloroethyl acrylate
O
H2C
O
H2C
O
H2C
O
H2C
408220-25G
408220-100G
99%
monomethyl ether hydroquinone,

100 ppm as inhibitor
M27301-5ML
M27301-250ML
M27301-1L
M27301-2L
M27301-18L
99%
MEHQ 10-20 ppm as inhibitor
E9706-100ML
E9706-1L
E9706-2L
99%
monomethyl ether hydroquinone,

10-60 ppm as inhibitor
234923-100ML
234923-1L
234923-18L
98%
hydroquinone 100 ppm as inhibitor
408905-25ML
408905-100ML
90%, technical grade
monomethyl ether hydroquinone

447315-100ML
447315-500ML
97%
MEHQ 200 as inhibitor
409693-250G
409693-1KG
98%

327182-5ML
327182-100ML
327182-1L
99%

436305-250ML
436305-1L
98%

0.001-0.11% as stabilizer
290815-25ML
290815-1L
290815-3L
290815-18L
>90%

437425-100ML
technical grade

424021-25ML
97%

474487-5ML
474487-25ML
96%

292818-250ML
292818-1L
292818-18L
95%
hydroquinone monomethyl ether

370932-1L
370932-18L
90%
hydroquinone 300 ppm as inhibitor

50 ppm as inhibitor
275573-25G
MEHQ, 900-1100 ppm as

inhibitor
552348-50ML
552348-500ML
98%
MEHQ, 2,000 ppm as inhibitor
330957-100ML
330957-500ML
technical grade

392103-100ML
392103-500ML
392103-1L
CH3
O
H2C
CH3
O
H 2C
OCH2(CH2)4CH3
Lauryl acrylate
O
H2C
Acrylate Monomers
97%
OCH3
Ethyl acrylate
Hexyl acrylate
Prod. No.
729817-5G
ONa
Methyl acrylate
Butyl acrylate
Additive
MEHQ, >100 ppm as inhibitor
Cl
Sodium acrylate
Purity
97%
OCH2(CH2)10CH3
Octadecyl acrylate
O
H2C
OCH2(CH2)16CH3
tert-Butyl acrylate
O
H2 C
Isobutyl acrylate
CH3
CH3
CH3
O
H2C
CH3
CH3
2-Ethylhexyl acrylate
O
H2C
CH3
CH3
Isooctyl acrylate
O
H2C
CH3
CH3
3,5,5-Trimethylhexyl
acrylate
H2C
1H,1H,2H,2H-Perfluorodecyl acrylate
H2C
CH3
O
OCH2CH2(CF2)7CF3
2-Hydroxyethyl acrylate
O
H2C
Hydroxypropyl acrylate,
mixture of isomers
O
H2C
4-Hydroxybutyl acrylate
CH3
O
O
CH3
OH
OH
O
H2 C
2-Carboxyethyl acrylate
OH
O
H2C
Isobornyl acrylate
OH
H2C
2-(Dimethylamino)ethyl
acrylate
CH3
CH3
CH3
O
O
OH
CH3
N
CH3
O
H2C
H3C CH3
CH3
O
O
38
Aldrich.com
CH2
Monomer Index
Name
Structure
Purity
Additive
Prod. No.
Pentabromophenyl
acrylate
Br
96%
592552-5G
98%
640263-1G
640263-5G
92%
475149-5ML
475149-25ML

1,000 ppm as inhibitor
408298-250ML
95%

407542-100ML

MEHQ 100 ppm as inhibitor
454990-250ML
454990-1L

469815-100ML
469815-500ML
Br
Br
Br
CH2
O
Br
Pentabromobenzyl
acrylate
Br
Br
CH2
Br
Br
Br
3-(Trimethoxysilyl)propyl
acrylate
OCH3
Si OCH3
OCH3
O
H2C
Di(ethylene glycol) ethyl

ether acrylate
O
H2C
Di(ethylene glycol)
2-ethylhexyl ether
acrylate
CH3
O
H2C
CH3
CH3
Poly(ethylene glycol)
methyl ether acrylate
O
H2C
Poly(propylene glycol)
acrylate
CH3
n
O
H2C
O H
CH3
Name
Structure
Average Mn
Additive (ppm)
Prod. No.

ether acrylate
2,000
MEHQ 3,500 as inhibitor

(may contain)
730270-1G
5,000

(may contain)
730289-1G
170.16
480797-5ML
480797-25ML
214.22
HQ 60-100 as inhibitor
MEHQ 90-150 as inhibitor
437433-100ML
302.32
HQ 100-150 as inhibitor
398802-250ML
398802-1L
258
475629-100ML
475629-500ML
575
437441-100ML
437441-500ML
700
BHT 300 as inhibitor

455008-100ML
455008-500ML
1,000

(may contain)
729086-1G
2,000

(may contain)
701971-1G
6,000
MEHQ, 1500 as inhibitor
701963-1G
10,000

(may contain)
729094-1G
H2C

ether acrylate
CH3
n
O
H2C
Ethylene glycol diacrylate
CH3
n
O
O
H2C
CH2
Acrylate Monomers
PEG Acrylate and Diacrylate Monomers
Di(ethylene glycol) diacrylate
O
H2C
Tetra(ethylene glycol)
diacrylate
diacrylate
O
O
O
O
O
O
H2C
CH2
O
n
O
O
H2C
CH2
O
n
O
O
H2C
CH2
O
n
O
O
H2C
CH2
O
n
diacrylate
CH2
O
n
diacrylate
CH2
O
O
H2C
O
O
H2C
O
CH2
diacrylate
O
O
H2C
diacrylate
diacrylate
CH2
O
H2C
diacrylate
CH2
39
Monomer Index
Polyfunctional Acrylate Monomers
Name
Structure
1,4-Butanediol diacrylate
Additive
Prod. No.
hydroquinone, ~75 ppm as inhibitor
411744-25ML
411744-100ML

246816-100G
246816-500G
CH2

246832-100G
246832-500G
CH2

246808-100G
246808-500G

246794-100G
246794-500G

408263-100ML
408263-250ML

407283-100ML
407283-500ML
O
O
H2C
CH2
1,6-Hexanediol diacrylate
O
O
H2C
CH2
Tri(propylene glycol) diacrylate,

mixture of isomers
O
H2C
Trimethylolpropane triacrylate
O(C3H6O)3
O
H2C
O
O
H3C
CH2
O
Pentaerythritol triacrylate
O
H2C
O
O
CH2
O
OH O
CH2
O
Pentaerythritol tetraacrylate
O
H 2C
H 2C
O
O
Acrylate Monomers
Dipentaerythritol penta-/
hexa-acrylate
RO
CH2
CH2
O
OR
CH2
R = H or *
OR OR OR OR
-Substituted Acrylate Monomers

Name
Structure
Purity
Prod. No.
98%
588466-1G
97%
302546-1G
302546-5G
95%
588458-1G
E1505-5G
E1505-10G
98%
425222-1G
425222-5G
98%
317519-1G
317519-5G
Methyl -bromoacrylate
H2C
OCH3
Br
Methyl 2-(bromomethyl)acrylate
O
Br
OCH3
CH2
tert-Butyl 2-bromoacrylate
O
H2C
O
Br
Ethyl 2-cyanoacrylate
CH3
CH3
CH3
O
H2 C
CH3
CH3
CN
Ethyl 2-(bromomethyl)acrylate
O
H2 C
Br
Methyl 2-acetamidoacrylate
H
N
H3C
O
40
Aldrich.com
O
OCH3
CH2
Monomer Index
Acrylamide Monomers
For a complete list of available acrylamide and methacrylamide monomers, visit Aldrich.com/acrylic.
Name
Structure
Acrylamide
N,N-Dimethylacrylamide
O
H2C
CH3
H2C
N
H
N-Isopropylacrylamide
O
N
H
N-tert-Butylacrylamide
monomethyl ether hydroquinone 500 as inhibitor
274135-5ML
274135-100ML
274135-500ML
97%
415324-10G
415324-50G
99%
731129-5G
731129-25G
97%
411779-100G
245801-100G
245801-1KG
97%
monomethyl ether hydroquinone 3,000 as stabilizer
697931-100ML
93%
364959-5G
364959-25G
95%
MEHQ as inhibitor
730149-25G
technical grade
436534-100ML
99%
222348-100G
222348-500G
technical grade
358878-5G
99%
530042-10G
96%
MEHQ 50
731145-5G
CH3
CH3
H2 C
CH3
N
H CH3
O
HO
CH2
N
H
N-Hydroxyethyl acrylamide
O
H2C
OH
N
H
OH
OH
N
H
OH
O
H2C
N
H
OCH3
O
H2 C
N
H
Diacetone acrylamide
CH3
CH3 O
O
H2C
CH3
N
H CH3
N,N-Ethylenebis(acrylamide)
H
N
H2C
N
H
N-Phenylacrylamide
CH3
O
H2C
Acrylamide Monomers
O
H2C
N-(Isobutoxymethyl)acrylamide
99%
CH3
CH3
H2C
N-(3-Methoxypropyl)acrylamide
Prod. No.
A8887-100G
A8887-500G
A8887-1KG
A8887-2.5KG
CH3
N
CH3
N-Isopropylacrylamide
N-[Tris(hydroxymethyl)methyl]
acrylamide
Additive (ppm)
-
CH2
H2N
N-(Hydroxymethyl)acrylamide
solution
Purity
99%
CH2
N
H
N-Diphenylmethylacrylamide
O
H2C
N
H
41
Monomer Index
Methacrylate Monomers
For a complete list of available methacrylate monomers, visit Aldrich.com/acrylic.
Monofunctional Methacrylate Monomers

Name
Structure
Glycidyl methacrylate
O
H2 C
F
F
O
H2C
MEHQ 1,500 ppm as inhibitor
741108-5G
741108-1G
4-tert-Butylcatechol ~280 ppm

as inhibitor
740950-5ML
740950-25ML
hydroquinone, 6,000 ppm

as stabilizer
735094-5G
>97%
733695-1G
733695-5G
>97%
733660-1G
733660-5G
97%
monomethyl ether hydroquinone ~100 ppm as inhibitor
730971-25G
98%
730300-1G
730300-5G
98%
730297-1G
97%
4-methylphenol 100 ppm as

inhibitor
730114-5G
95%
MEHQ, >1,000 ppm
729841-25G
95%
MEHQ ppm as inhibitor
729833-25G
97%
monomethyl ether hydroquinone, ~200 ppm as stabilizer
523216-100ML
523216-1L
99%
408212-50G
408212-250G
Solketal methacrylate
O
H2C
CH3
CH3
CH3
CH3
O
O
95%
F
CH3
1,1,1-Trifluoro-2-(trifluoromethyl)-2hydroxy-4-methyl-5-pentyl
methacrylate
Prod. No.
779342-100ML
779342-500ML
Pentafluorophenyl methacrylate
H2C
Additive
hydrochinone monomethylether
~0.01% (w/v) as stabilizer
O
CH3
Bis(2-methacryloyl)oxyethyl disulfide
Purity
97.0%, GC
CH2
CH3
CH3
H3C HO CF3
O
H2C
CF3
2-[(1,1,1-Trifluoro-2-(trifluoromethyl)2-hydroxy)propyl]-3-norbornyl
methacrylate
HO CF3
CF3
O
CH2
CH3
2-(Diisopropylamino)ethyl
methacrylate
H3C
O
H2C
CH3
N
CH3
CH3
CH3
Methacrylic acid N-hydroxysuccinimide

ester
O
O
H2C
O
CH3
TEMPO methacrylate
O
CH2
CH3
H3C
CH3
N
O
H3C
2-Methacryloyloxyethyl phosphorylcholine
O
H2C
O
O P O
O
O
CH3
Triethylene glycol methyl ether

methacrylate
CH3
CH3
N CH3
CH3
CH3
O
H2C
OCH3
2-N-Morpholinoethyl methacrylate
O
CH2
O
N
CH3
Methacryloyl chloride
O
H2C
Cl
CH3
Sodium methacrylate
O
H2C
ONa
CH3
42
Aldrich.com
Monomer Index
Name
Structure
Methacrylic acid
Purity
Additive
Prod. No.
99%
MEHQ, 250 ppm as inhibitor
155721-5G
155721-100G
155721-500G
155721-2KG
155721-3KG
155721-18KG
99%
MEHQ, 30 ppm as inhibitor
M55909-25ML
M55909-500ML
M55909-1L
M55909-2L
M55909-17L
99%
monomethyl ether hydroquinone, 15-20 ppm as inhibitor
234893-100ML
234893-500ML
234893-1L
99%
373761-5G
373761-25G
99%
monomethyl ether hydroquinone 10 ppm as inhibitor
235865-5ML
235865-100ML
235865-1L
235865-18L
98%
MEHQ, 100 ppm
462373-500G
462373-1KG
96%
291811-100ML
291811-500ML
technical grade
monomethyl ether hydroquinone 300-500 ppm as inhibitor
411442-250ML
411442-1L
98%
463353-100ML
463353-250ML
97%
169919-1L
169919-18L
98%
monomethyl ether hydroquinone ~50 ppm as stabilizer
290807-25ML
290807-1L
99%
477028-25ML
477028-100ML
97%
128635-5G
128635-500G
128635-1KG
128635-18KG
97%
268542-100ML
268542-1L
268542-18L
90%
phenothiazine ~500 ppm as

stabilizer
516155-5G
516155-25G
CH3
N
CH3
98%
monomethyl ether hydroquinone 2,000 ppm as inhibitor
234907-100ML
234907-1L
CH3
99%
phenothiazine 100 ppm as inhibitor
408980-250ML
408980-1L
98%
BHT <0.1% (w/v) as inhibitor
477060-5ML
477060-50ML
98%
MEHQ 50-185 ppm as inhibitor
234931-100ML
234931-500ML
O
H2C
OH
CH3
Methyl methacrylate
O
H2C
OCH3
CH3
Ethyl methacrylate
O
H2 C
CH3
CF3
CH3
2,2,2-Trifluoroethyl methacrylate
O
H2C
CH3
Butyl methacrylate
O
H 2C
CH3
CH3
Hexyl methacrylate
O
H2C
OCH2(CH2)4CH3
CH3
Lauryl methacrylate
O
H2 C
OCH2(CH2)10CH3
CH3
Stearyl methacrylate
O
OCH2(CH2)16CH3
CH3
tert-Butyl methacrylate
O
H2C
O
CH3
Isobutyl methacrylate
CH3
CH3
CH3
O
H2C
CH3
2-Ethylhexyl methacrylate
CH3
CH3
O
H2C
CH3
CH3
H2C
CH3
2-Hydroxyethyl methacrylate
O
H2C
OH
O
CH3
2-Hydroxyethyl methacrylate
O
H2C
OH
O
CH3
Hydroxypropyl methacrylate
H2C
OC3H6OH
CH3
2-Aminoethyl methacrylate hydrochloride
O
H2 C
CH3
2-(Dimethylamino)ethyl methacrylate
NH2
HCl
O
H3C
O
CH2
2-(Diethylamino)ethyl methacrylate
O
H2C
CH3
CH3
2-Isocyanatoethyl methacrylate
O
H2 C
NCO
CH3
Allyl methacrylate
O
H2C
CH2
CH3
43
Monomer Index
Name
Structure
Glycidyl methacrylate
O
H2 C
Purity
Additive
Prod. No.
97%
151238-100G
151238-500G
97%
411760-25ML
411760-100ML
96%
409448-250ML
409448-1L
97%
monomethyl ether hydroquinone ~60 ppm as inhibitor
408964-100ML
408964-250ML
98%
251658-100G
251658-500G
technical grade
392111-100ML
392111-500ML
392111-1L
659576-25ML
95%, NMR
Ionol 46 (Raschig GmbH) as

inhibitor
700479-1G
96%
347485-25G
347485-100G
98%
440159-100ML
440159-500ML
O
O
CH3
Furfuryl methacrylate
CH3
O
CH2
O
Benzyl methacrylate
O
H2 C
O
CH3
Cyclohexyl methacrylate
O
H2 C
O
CH3
3-Sulfopropyl methacrylate potassium

salt
O
S OK
O
O
H2C
O
CH3
Isobornyl methacrylate
CH3
CH2 H3C
CH3
O
H3C
Glycosyloxyethyl methacrylate solution

5% (w/v) in ethanol
HO
CH3
O
OH
O
OH
Ferrocenylmethyl methacrylate
CH3
O
CH2
O
OH
Fe
2-(Trimethylsilyloxy)ethyl methacrylate
CH2
O
CH3
O Si CH3
CH3
O
H2C
O
CH3
3-(Trimethoxysilyl)propyl methacrylate
OCH3
H3CO Si
OCH3
O
CH2
CH3
PEG Methacrylate Monomers

Name
Structure
Triethylene glycol methyl ether

methacrylate
CH3
O
H2C
Average Mn
Additive (ppm)
Prod. No.
232.27
MEHQ, >1,000
729841-25G
300

447935-100ML
447935-500ML
475

447943-100ML
447943-500ML
950

447951-100ML
447951-500ML
2,000
730319-1G
5,000
730327-1G
~2,080
457876-250ML
457876-1L
OCH3

ether methacrylate
O
H2C
O
n
CH3

ether methacrylate
O
H2C
O
H2C
O
H2C
O
H2C
O
H2C
O
CH3
44
Aldrich.com
CH3
n
CH3

ether methacrylate
CH3
n
CH3

ether methacrylate
CH3
n
CH3

ether methacrylate
CH3
n
CH3

ether methacrylate
CH3
CH3
n
Monomer Index
Polyfunctional Methacrylate Monomers
Name
Structure
Bis(2-methacryloyl)oxyethyl
disulfide
CH3
O
O
H 2C
Additive (ppm)
Prod. No.
hydroquinone, 6,000 as
stabilizer
735094-5G
90%
monomethyl ether hydroquinone 700-1,000
695890-100ML
695890-250ML
95%
234958-100G
234958-500G
90%
hydroquinone 100 as
inhibitor
411736-100ML
436895-100ML
436895-500ML
97%
topanol 22525 as inhibitor
436909-100ML
436909-500ML
technical grade
246840-100G
246840-500G
CH2
Phosphoric acid 2-hydroxyethyl

methacrylate ester
Purity
CH3
R=* H
O
and / or O
RO P OR
OR
R=*
O
CH2
CH3
1,4-Butanediol dimethacrylate
CH3
O
O
H 2C
CH2
1,6-Hexanediol dimethacrylate
CH3
O
CH3
O
H2C
CH2
CH3
Glycerol dimethacrylate,
mixture of isomers
O
H2C
O
O
OR
CH3
Diurethane dimethacrylate,
mixture of isomers
OR
O
H2C
CH2
R = H or *
H
N
CH3
CH3
CH3 CH3
R
CH3
N
H
CH2
O
R = H or CH3 (~1:1)
O
CH2
H 3C O
CH3
O
H 2C
CH3
H 3C
O
CH2
Methacrylamide Monomers
For a complete list of available acrylamides and methacrylamide monomers, visit Aldrich.com/acrylic.
Name
Structure
Methacrylamide
O
H2C
Purity
Prod. No.
98%
109606-5G
109606-250G
109606-500G
97%
423548-25G
99%
409472-250ML
409472-1L
98%
566225-100MG
566225-500MG
595845-1G
NH2
CH3
N-Isopropylmethacrylamide
O
H2C
CH3
N-[3-(Dimethylamino)propyl]methacrylamide
CH3
N
H
CH3
O
H2 C
CH3
N
H
7-[4-(Trifluoromethyl)coumarin]methacrylamide
CH3
N
CH3
CF3
O
H2C
CH3
Disperse Orange 3 methacrylamide

O2N
N
H
N
N
Methacrylamide Monomers
Trimethylolpropane
trimethacrylate
O
N
H
CH2
CH3
45
Monomer Index
Vinyl Amide and Vinyl Ester Monomers

For a complete list of available vinyl monomers, visit Aldrich.com/monomers.
Name
Structure
Purity
Additive
Prod. No.
N-Vinylformamide
98%
4-Hydroxy-TEMPO 25-55 ppm

as stabilizer
447331-100ML
447331-500ML
98%
255130-100ML
255130-500ML
98%

<100 ppm as inhibitor
401714-500ML
99%

6-15 ppm as stabilizer
124400-250ML
124400-1L

5 ppm as inhibitor
134481-1L
>99%
411795-10G
95%
436208-50G
436208-250G
99%
528064-5ML
528064-10ML
99%
hydroquinone 20 ppm
as stabilizer
403091-100ML
403091-500ML
N
H
N-Methyl-N-vinylacetamide
CH2
O
H3C
N
CH2
CH3
Vinyl propionate
O
H3C
Vinyl pivalate
CH2
O
t-Bu
Vinyl neodecanoate, mixture of

isomers
CH2
O
C9H19
Vinyl decanoate
CH2
O
CH3(CH2)7CH2
Vinyl stearate
Vinyl chloroformate
Vinyl Amide and Vinyl Ester Monomers
CH2
CH2
O
O
Aldrich.com
O
Cl
46
CH2
O
CH3(CH2)15CH2
Vinyl benzoate
CH2
Materials Science
Polymer Center of Excellence

Custom Services
Aldrich Materials Science has established a Center of Excellence in Polymer

Science with expertise in the research and development of custom polymers
and monomers. The Polymer Center of Excellence prepares specialty
monomers and polymers for researchers through the catalog and serves
applied markets from research through development to commercial-scale
manufacturing.
Polymer Chemistry Capabilities:

yy Custom polymer/monomer research and synthesis
yy Expertise in the synthesis of high-purity monomers, initiators
and specialty polymers

- Traditional free radical polymerization
- C
ontrolled free radical polymerization including Reversible
Addition/Fragmentation Chain Transfer (RAFT)*
- Condensation polymerization
- Ionic polymerization
- Ring-opening polymerization
- End-group functionalization/conjugation
- Lyophilization/purification
yy State-of-the-art analytical suite, including GPC, viscometry, DSC
yy ISO 9001 and cGMP quality systems
*Sigma-Aldrich is pleased to offer custom synthesis of well-defined polymers via CSIROs

patented RAFT Technology. Controlled Radical Polymerization via RAFT enables a range of
unique copolymers with complex architectures such as diblocks, triblocks, stars, grafts, gradients
and branched.
For more information, visit Aldrich.com/matsci
For more information on capabilities

or to request a quote, contact us at
[email protected]

R1
O
R2
Styrenes
H
N
Acrylates
Acrylamides
Methacrylates
Methacrylamides
Vinyl Esters
Structure
C12H25S
CN
OH
N
H
723037
CH3
CH3
Aldrich
Prod. No.
723274
H
N
Vinyl Amides
Styrenes
Acrylates
Acrylamides
Methacrylates
Methacrylamides
Vinyl
Esters
Vinyl
Amides
+++
++
++
+++
+++
+++
++
++
+++
+++
+++
++
++
+++
+++
+++
++
++
+++
+++
+++
++
++
+++
+++
+++
++
++
+++
+++
+++
++
++
+++
+++
++
++
++
+++
+++
++
++
++
+++
+++
+++
+++
+++
++
+++
+++
++
+++
+++
++
+++
+++
++
+++
+++
++
+++
+++
++
+++
+++
++
+++
+++
C12H25S
CN
760110
S
H3C(H2C)10H2C
753033
CN
OH
S H3C CN
H3C(H2C)10H2C
O
n
752487
S H3C CN
H3C(H2C)10H2C
751634
S H3C CN
H3C(H2C)10H2C
751626
S H3C CN
H3C(H2C)10H2C
731269
S
S
751138
S
O
S
O
731277
S
S
CN
NC
722995
O
S
OH
CN
722987
S
S
760439
CN
S
S
741701
S
O
S
O
761257
S
O
S
O
758353
CN
O
O
O
760455
S
O
S
O
+++ = Well suited
= Poorly suited

R1
O
R2
Styrenes
H
N
CH3
CH3
O
H
N
Acrylates
Acrylamides
Methacrylates
Methacrylamides
Vinyl Esters
Aldrich
Prod. No.
Structure
749133
S
H3C(H2C)10H2C
CH3
Vinyl Amides
Styrenes
Acrylates
Acrylamides
Methacrylates
Methacrylamides
Vinyl
Esters
Vinyl
Amides
++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
+++
OH
N
H
723010
S
C12H25
OH
S
O
740497
S
C12H25
OCH3
S
O
741035
S
C12H25
O
O
752495
S H3C CH3
H3C(H2C)10H2C
O
n
753025
S H3C
H3C(H2C)10H2C
CH3
O
O
n
H3C
741698
H3C(H2C)10H2C
CH3
S H3C CH3
O
S
O
CH2(CH2)10CH3
N3
740810
F
F
O
S
H3C(H2C)H2C
F
F
O
F
740705
O
O
O
n
739367
C12H25
S
O
O
n
736325
C12H25
S
O
O
n
741728
S H3C
H3C(H2C)10H2C
C12H25
CH3
O
O
n
H3C
723029
C12H25S
S
CH3
CN
CH3
N
S
CN
CH2(CH2)10CH3
723002
751200
S
N
753106
CN
S
N
+++ = Well suited
= Poorly suited
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Controlled Radical Polymerization Guide

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Controlled Radical

Chain-growth polymerization has been successfully performed

yyAtom Transfer Radical Polymerization (ATRP)

Table 1. Benefits and limitations of ATRP, RAFT, and NMP processes.

yyNo use of transition

yyAbility to tailor catalyst yyNo use of transition

yyHigh potential for odor yyLeast versatile

Polymers generated by controlled radical polymerization are used

All of these technologies are popular in the research community

yyLow potential for odor

#2757 CRP, TOC, edited 0228

ATRP for Everyone: Ligands and Initiators for the

Block Copolymer Synthesis Using a Commercially

Authors: Jakubowski, Tsarevsky, McCarthy, and

Tools for Performing ATRP.............................................................................. 6

Authors: Lee, Wooley

Copper(I)-mediated Living Radical Polymerization in

Typical Procedures for Polymerizing via ATRP ............................. 11

Applying ARGET ATRP to the Growth of Polymer

ARGET ATRP: Procedure for PMMA Polymer

Monomer Index ......................................................................35

Atom Transfer Radical Polymerization (ATRP) ........... 2

Authors: Zhu, Edmondson

Reversible Addition/Fragmentation Chain

Concepts and Tools for RAFT Polymerization............................... 22

Typical Procedures for Polymerizing via RAFT ............................. 23

Universal/Switchable RAFT Agents for Well-defined

Polymerization Procedure with Universal/Switchable

ATRP for Everyone: Ligands and Initiators

Wojciech Jakubowski, Nicolay V. Tsarevsky, Patrick McCarthy*, Krzysztof Matyjaszewski

Scheme 1. Schematic illustration of the ATRP process (top) and an example of

ATRP is a catalytic process using a metal complex, in which the transition

Figure 1. Ligands for Cu-mediated ATRP using ppm amounts of catalyst.

ATRP for Everyone: Ligands and Initiators

*Note: Time of the reaction may vary depending on a type of used

Typical ICAR ATRP Procedure

Polymerization conditions for ICAR ATRP of styrene:

Molecular weight [g/mol]

Molecular weight [g/mol]

It is interesting to compare the results of ICAR ATRP employing Me6TREN

seen from Table 1, only the polymerizations mediated by the complexes

Figure 3 presents GPC traces of polystyrene-b-poly(t-butyl acrylate)

ATRP for Everyone: Ligands and Initiators

Figure 3. GPC traces and properties of PSt-b-PtBA block copolymer library.

Initiators for ATRP

where [M]0 is the initial monomer concentration, [RX]0 is the initial

Biodegradable (disulfide) initiator

Mn = ([M]0 / [RX]0) Conv MW(M)

Monomer M: styrene, acrylate,

FG: hydroxyl group

ATRP for Everyone: Ligands and Initiators

Br: bromine group

Figure 4. Examples of ATRP initiators yielding polymeric stars.

Br: bromine group

FG: disulfide group

Br: bromine group

Figure 6. Examples of end-functionalized polymers prepared by ATRP using an initiator

A much broader variety of functional alkyl halides can be easily

ATRP for Everyone: Ligands and Initiators

Tools for Performing ATRP