Synthesis of Nanocomposite Organic/Inorganic Hybrid

Materials Using Controlled/LivingRadical

Polymerization
Jeffrey Pyun and Krzysztof Matyjaszewski *
Center for Macromolecular Engineering, Department of Chemistry, CarnegieMellon
University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213
Received February 16, 2001
The preparati on of hybri d organi c/i norgani c nanocomposi tes compri sed of wel l -defi ned
pol ymers was revi ewed. I n parti cul ar, syntheti c methods usi ng control l ed/l i vi ng radi cal
pol ymeri zati on techni ques, such as stabl e free-radi cal /ni troxi de-medi ated pol ymeri zati ons,
atom transfer radi cal pol ymeri zati on, and reversi bl e addi ti on-fragmentati on chai n-transfer
pol ymeri zati on were descri bed. The vari ous approaches taken to prepare hybri d copol ymers,
nanoparti cl es, pol ymer brushes, di spersed si l i cate nanocomposi tes, and nanoporous materi al s
were di scussed.
1. Introduction
The synthesi s of novel materi al s wi th i mproved
properti es and performance i s a conti nual l y expandi ng
fronti er at the i nterface of chemi stry and materi al s
sci ence. I n thi s pursui t, the abi l i ty to control mol ecul ar
structure on atomi c and macroscopi c di mensi ons i s a
key parameter i n desi gni ng materi al s wi th prepro-
grammed acti vi ty. A si gni fi cant advance i n thi s area has
been the synthesi s of nanocomposi tes where the struc-
tural order wi thi n the materi al can be control l ed on
nanometer/submi cron scal es. Whi l e materi al s possess-
i ng such structural compl exi ty are common i n nature,
robust and versati l e methods to prepare syntheti c
nanocomposi tes remai ns an exci ti ng chal l enge that i s
bei ng tackl ed by research groups around the worl d.
1
One approach to prepare nanocomposi tes has been the
i ncorporati on of wel l -defi ned organi c and i norgani c
components i nto a si ngul ar materi al . I n parti cul ar, the
i ncl usi on of wel l -defi ned pol ymers to i norgani c sub-
strates i s of si gni fi cance, because the functi onal i ty,
composi ti on, and di mensi ons of these macromol ecul es
enabl e the desi gn of speci fi c properti es i nto the resul ti ng
hybri d.
2
Wel l -defi ned organi c pol ymers have been attached to
i norgani c (co)pol ymers, parti cl es, surfaces, gl assy net-
works and i nterpenetrati ng pol ymer networks to pre-
pare organi c/i norgani c hybri d materi al s. Addi ti onal l y,
pol ymers of control l ed si ze, composi ti on, and archi tec-
ture have been used as shape templ ates i n the synthesi s
of mesoporous i norgani c networks (Fi gure 1). Pol ymers,
such as pol y(tetramethyl ene oxi de) and pol y(oxazol i nes),
have been used to synthesi ze hybri d organi c/i norgani c
nanocomposi tes.
3
However, recent devel opments i n
control l ed/l i vi ng radi cal pol ymeri zati on (CRP) have
provi ded another val uabl e methodol ogy to i ntroduce
wel l -defi ned organi c (co)pol ymers to a vari ety of i nor-
gani c substrates. The scope of thi s revi ew wi l l cover
hybri d organi c/i norgani c nanocomposi tes that have been
made usi ng CRP. For more fundamental di scussi ons of
organi c/i norgani c hybri d materi al s, the reader i s di -
rected to other revi ews.
2-5
2. Controlled Radical Polymerization
CRP has proved to be a versati l e and robust method
to prepare wel l -defi ned organi c pol ymers. I n the past
decade, several techni ques have been devel oped to
synthesi ze wel l -defi ned pol ymers vi a radi cal pol ymer-
i zati on. A major di fference between conventi onal radi cal
[i .e., azobi s(i sobutyroni tri l e)- or peroxi de-i ni ti ated pro-
cesses] and control l ed radi cal pol ymeri zati ons i s the
l i feti me of the propagati ng radi cal duri ng the course of
the reacti on. I n conventi onal radi cal processes, radi cal s
generated by decomposi ti on of the i ni ti ator undergo
propagati on and bi mol ecul ar termi nati on reacti ons
wi thi n a second. I n contrast, the l i feti me of a growi ng
radi cal can be extended to several hours i n a CRP,
enabl i ng the preparati on of pol ymers wi th predefi ned
mol ar masses, l ow pol ydi spersi ty, control l ed composi -
ti ons, and functi onal i ty.
6,7
The mechani sm i nvoked i n CRP processes to extend
the l i feti me of growi ng radi cal s uti l i zes a dynami c
equi l i brati on between dormant and acti ve si tes wi th
Figure 1. Exampl es of organi c/i norgani c hybri d materi al s.
3436 Chem. Mater. 2001, 13, 3436-3448
10.1021/cm011065j CCC: $20.00 2001 Ameri can Chemi cal Soci ety
Publ i shed on Web 08/03/2001
rapi d exchange between the two states. Unl i ke conven-
ti onal radi cal processes, CRP requi res the use of per-
si stent radi cal (deacti vator) speci es, or hi ghl y acti ve
transfer agents to react wi th propagati ng radi cal s.
These persi stent radi cal s/transfer agents react wi th
radi cal s (deacti vati on or transfer reacti ons wi th rate
constant, k
d
) to form the dormant speci es. Conversel y,
propagati ng radi cal s are generated from the dormant
speci es by an acti vati on reacti on (wi th rate constant,
k
a
).
2.1. Classification of CRP Systems. I n the past
decade, the fi el d of CRP has seen tremendous devel op-
ment as evi denced by the wi de range of materi al s that
have been prepared usi ng these techni ques. I n parti cu-
l ar, three methods of consi derabl e i mportance are the
fol l owi ng: stabl e free-radi cal pol ymeri zati on [SFRP;
e.g., ni troxi de-medi ated processes (NMP)], metal -cata-
l yzed atom transfer radi cal pol ymeri zati on (ATRP), and
degenerati ve transfer [e.g., reversi bl e addi ti on-frag-
mentati on chai n transfer (RAFT)]. Whi l e these three
systems possess di fferent components, general si mi l ari -
ti es i n the CRP processess can be seen i n the use of
i ni ti ators, radi cal medi ators (i .e., persi stent radi cal s or
transfer agents), and i n some cases catal ysts (Scheme
1). I t i s i mportant to note that whi l e SFRP and ATRP
are subject to the persi stent radi cal effect (PRE),
8,9
degenerati ve processes, such as RAFT, do not conform
to the PRE model because of the transfer-domi nated
nature of the reacti on.
2.1.2. SFRP. I n thi s type of CRP, al koxyami ne
i ni ti ators
10
(-P
n
X; eq 1 i n Scheme 1) and ni troxi de
persi stent radi cal s (X
0
; eq 1 i n Scheme 1) have been
effecti vel y used to pol ymeri ze styrenes and acryl ates.
I n certai n systems, al koxyami nes have al so been gener-
ated i n si tu by the i ni ti al use of conventi onal radi cal
i ni ti ators (AI BN and peroxi des) and ni troxi de persi stent
radi cal s, whi ch al so l ed to a CRP process.
11
A wi del y
used ni troxi de i n the pol ymeri zati on of styrene (Sty) i s
2,2,6,6-tetramethyl pi peri di nyl oxy (TEMPO), al though
recentl y devel oped ni troxi des can al so pol ymeri ze acry-
l ates i n a control l ed fashi on.
12,13
The current l i mi tati on
i n thi s system l i es i n the i nabi l i ty to successful l y
pol ymeri ze methacryl ate monomers, because of -hy-
drogen el i mi nati on to the ni troxi de radi cal s. Addi ti on-
al l y, thi uram di sul fi des and di thi ocarbamate i ni ferter
systems have been used as agents for CRP wi th l i mi ted
success.
14,15
2.1.3. ATRP. I n these pol ymeri zati ons, radi cal s are
generated by the redox reacti on of al kyl hal i des (-P
n
X;
eq 2 i n Scheme 1) wi th transi ti on-metal compl exes (Y;
eq 2 i n Scheme 1).
16-18
Radi cal s can then propagate but
are rapi dl y deacti vated by the oxi di zed form of the
transi ti on-metal catal yst (X-Y
0
; eq 2 i n Scheme 1).
I ni ti ators typi cal l y used are R-hal oesters (e.g., ethyl
2-bromoi sobutyrate and methyl 2-bromopropi onate) or
benzyl hal i des (e.g., 1-phenyl ethyl bromi de and benzyl
bromi de). A wi de range of transi ti on-metal compl exes,
such as Ru-, Cu-, and Fe-based systems, have been
successful l y appl i ed to ATRP. For Cu-based systems,
l i gands such as 2,2-bi pyri di ne and al i phati c ami nes
have been empl oyed to tune both the sol ubi l i ty and
acti vi ty of vari ous ATRP catal ysts. ATRP has been
successful l y appl i ed for the control l ed pol ymeri zati on
of styrenes, (meth)acryl ates, (meth)acryl ami des, acry-
l oni tri l e, and 4-vi nyl pyri di ne. ATRP systems are cur-
rentl y l i mi ted to monomers that do not strongl y coor-
di nate to the catal yst.
18
2.1.4. DegenerativeTransfer. Radi cal pol ymeri za-
ti ons based upon a degenerati ve transfer system rel y
upon the rapi d and reversi bl e exchange of hi ghl y acti ve
transferabl e groups (-X; eq 3 i n Scheme 1) and growi ng
pol ymeri c radi cal s (-P
m
0
and -P
n
0
; eq 3 i n Scheme 1).
Whi l e conventi onal radi cal i ni ti ators (AI BN and perox-
i des) are used i n thi s reacti on, these compounds onl y
serve as a radi cal source to dri ve reversi bl e exchange
reacti ons between acti ve and dormant states. Transfer
agents i n thi s process contai n moi eti es for both i ni ti ati on
and transfer whi ch are generated i n the presence of
radi cal s. Control l ed radi cal pol ymeri zati ons from de-
generati ve transfer reati ons have been done usi ng al kyl
iodides,
19
unsaturated methacrylate esters,
20
or thioesters
as the transfer agents. I n parti cul ar, the use of thi oesters
i n the radi cal pol ymeri zati on of vi nyl monomers resul ts
i n a RAFT pol ymeri zati on.
21
The RAFT process has
proven to be a versati l e method to pol ymeri ze functi onal
styrenes, (meth)acryl ates, and vi nyl esters.
2.2. Synthetic Methodologies ToPrepareNano-
composite Hybrids Using CRP. A vari ety of CRP
techni ques have been devel oped to i ncorporate wel l -
defi ned organi c pol ymers to i norgani c substrates. A key
advantage of CRP processes i s the faci l e functi onal i za-
ti on/deposi ti on of i ni ti ator and pol ymeri zabl e moi eti es
onto i norgani c pol ymers and surfaces.
2.2.1. Synthesis of Hybrid Homopolymers and
Block, Graft, and Random Copolymers. I n the
preparati on of organi c/i norgani c nanocomposi te materi -
al s, hybri d copol ymers are of parti cul ar i nterest because
of the i nherent i ncompati bi l i ty of the two segments.
Thus, phase separati on of these segments yi el ds a
vari ety of control l ed nanostructures dependi ng on the
degree of i ncompati bi l i ty of the components, the com-
posi ti on, and the degree of pol ymeri zati on i n the fi nal
copol ymer.
A wi de range of pol ymeri c structures have been made
usi ng di fferent combi nati ons of organi c and i norgani c
components. I n the si mpl est case, a vi nyl monomer
possessi ng an i norgani c moi ety (R ) i norgani c moi ety;
Scheme 2a) can be homopol ymeri zed i n the presence of
i ni ti ator (R-X) to prepare a hybri d homopol ymer wi th
Scheme 1. Classification and General Mechanism
of CRP Methods for (1) SFRP, X ) O-NR
2
, (2)
ATRP, X ) Halogen, Y ) M
t
n
/L
n
, Y
0
) X-M
t
n+1
/L
n
,
(3) Degenerative Transfer, Reversible
Addition-Fragmentation Chain-Transfer
Polymerizations, X ) I, -SC )
(Z)-S-CH(R)-CH
2
-R
Reviews Chem. Mater., Vol. 13, No. 10, 2001 3437
organi c mai n-chai n and i norgani c si de-chai n groups.
Al ternati vel y, i norgani c vi nyl monomers can be copo-
l ymeri zed i n the presence of organi c monomers and R-X
to make random copol ymers (Scheme 2b). Chai n exten-
si on of an organi c macroi ni ti ator prepared by CRP wi th
an i norgani c monomer yi el ds a bl ock copol ymer (Scheme
2c). Conversel y, an i norgani c macroi ni ti ator can be used
i n the CRP of an organi c vi nyl monomer to al so prepare
a hybri d bl ock copol ymer (Scheme 2d). I norgani c mac-
roi ni ti ators can be synthesi zed by end-cappi ng growi ng
i norgani c chai n ends obtai ned from i oni c or step-growth
processes wi th coupl i ng agents that contai n CRP i ni ti a-
tor groups. I n a si mi l ar fashi on, hybri d graft copol ymers
are prepared by chai n extendi ng a mul ti functi onal
i norgani c macroi ni ti ator wi th an organi c vi nyl monomer
(Scheme 2e). Addi ti onal l y, i norgani c macromonomers
possessi ng vi nyl end groups can be copol ymeri zed wi th
organi c vi nyl monomers by CRP, yi el di ng graft copol y-
mers wi th organi c mai n-chai n and i norgani c si de-chai n
groups (Scheme 2f).
2.2.2. Synthesis of Hybrid Polymers fromInor-
ganic Initiators. Another type of hybri d pol ymer i s
prepared by the use of a (mul ti )functi onal i norgani c
compound as an i ni ti ator for CRP. Vari ous pol ymeri c
structures are possi bl e dependi ng on the functi onal i ty
of the i ni ti ator. Monofuncti onal i norgani c i ni ti ators
woul d resul t i n an end-functi onal pol ymer, whi l e mul -
ti functi onal i ni ti ators yi el d branched/star pol ymers
(Scheme 3).
2.2.3. Synthesis of Nanocomposite Particles,
Modified Surfaces, Dispersed Silicates, and Nan-
oporous Materials. The tetheri ng of wel l -defi ned
organi c pol ymers to i norgani c substrates such as par-
ti cl es (Scheme 4a) and surfaces (Scheme 4b) can be
conducted usi ng CRP. The attachment of prepared
pol ymers was achi eved by grafti ng to curved and fl at
surfaces.
22-26
However, by the use of CRP methods,
grafti ng organi c pol ymers from surfaces can be per-
formed by attachment of an i ni ti ator group (-X; Scheme
4) and pol ymeri zati on of a vi nyl monomer. The chem-
i stry requi red for the functi onal i zati on of CRP i ni ti ator
groups on curved and fl at surfaces depends on the type
of i norgani c substrate used. I n the case of gol d and
si l i con wafers, the i ncorporati on of i ni ti ati ng moi eti es
to surfaces requi res the tetheri ng of functi onal thi ol s,
or chl oro/al koxysi l anes, respecti vel y. By the use of CRP
from i norgani c surfaces, ul trathi n fi l ms of preci se thi ck-
ness and composi ti on can be grown. Organi c/i norgani c
nanocomposi tes can al so be prepared by CRP from the
surfaces of l ayered si l i cates (Scheme 4c). CRP of an
organi c vi nyl monomer between the i norgani c l ayers
yi el ds a nanocomposi te of i norgani c pl atel ets di spersed
i n a matri x of wel l -defi ned pol ymer. Fi nal l y, pol ymers
of control l ed si ze and composi ti ons can be prepared by
CRP and used as templ ates i n the network pol ymeri -
zati on of i norgani c resi ns (Scheme 4d). When the mol ar
mass and composi ti on of the pol ymer templ ate are
tuned, usi ng CRP enabl es control of both the hydrody-
nami c vol ume and the compati bi l i ty of the pol ymer wi th
Scheme 2. Synthetic Approaches To Prepare
Hybrid Polymers
Scheme 3. Hybrid Polymers Prepared Using
Inorganic Initiators
Scheme 4. Examples of Hybrid Materials Prepared
fromParticles, Flat Surfaces, Layered Silicates,
and Networks
3438 Chem. Mater., Vol. 13, No. 10, 2001 Reviews
the i norgani c matri x, respecti vel y. Network formati on
around the pol ymeri c templ ates, fol l owed by degrada-
ti on of the organi c components, yi el ds an i norgani c gl ass
wi th nanosi zed pores di spersed throughout the materi al .
3. Silicon-Containing Hybrid Homopolymers
and Block and Graft Copolymers
3.1. Synthesisof Poly(dimethylsiloxane) (PDMS)
Block and Graft Copolymers. The synthesi s of co-
pol ymers contai ni ng both PDMS and pol ystyrene/pol y-
((meth)acryl ates) was conducted from a vari ety of
approaches. Copol ymers contai ni ng PDMS and organi c
pol ymers are of i nterest, because the i nherent i ncom-
pati bi l i ty of the components i nduces phase-separated
structures of nanometer di mensi ons. These materi al s
have anti ci pated appl i cati ons as thermopl asti c el as-
tomers, si l i cone rubbers, and surfactants for supercri ti -
cal CO
2
.
27
To prepare these structures, PDMS com-
pounds prepared from both l i vi ng ani oni c pol ymeri zati on
and condensati on processes were functi onal i zed wi th
ei ther i ni ti ator groups or pol ymeri zabl e moi eti es for
CRP.
3.1.1. Synthesis of ABA and ABC Triblock Co-
polymersContainingPDMS. A di rect and conveni ent
approach to prepari ng ABA tri bl ock copol ymers i s the
functi onal i zati on of tel echel i c PDMS wi th i ni ti ator end
groups and appl i cati on of the macroi ni ti ator to CRP
systems. Tel echel i c PDMS compounds wi th di fferent
ki nds of end groups are readi l y prepared by condensa-
ti on pol ymeri zati ons and are commerci al l y avai l abl e.
Di functi onal PDMS wi th ei ther vi nyl or si l ane (Si -H)
end groups can be reacted wi th vari ous al kenes vi a
hydrosi l ati on to i ntroduce functi onal i ty to the PDMS
chai n ends.
27
Usi ng thi s general approach, PDMS mac-
roi ni ti ati ors for ATRP were made by the hydrosi l ati on
of tel echel i c PDMS (M
n
)9800; M
w
/M
n
)2.4) possessi ng
vi nyl end groups wi th [2-[4-(chl oromethyl )phenyl ]ethyl ]-
di methyl si l ane (a i n Scheme 5). The ATRP of Sty from
the benzyl chl ori de functi onal PDMS yi el ded an ABA
tri bl ock copol ymer of p(Sty-b-DMS-b-Sty) (M
n
) 20 700;
M
w
/M
n
) 1.6).
28
Al ternati vel y, PDMS macroi ni ti ators beari ng ami ne
end groups were reacted wi th 2-bromoi sobutyryl bro-
mi de to prepare di functi onal PDMS macroi ni ti ators for
ATRP. These macroi ni ti ators were then used i n the
ATRP of 2-(di methyl ami no)ethyl methacryl ate to pre-
pare an ABA tri bl ock copol ymer, wi th PDMS as the
mi ddl e segment.
29
ABC tri bl ock copol ymers were synthesi zed by trans-
formati on of l i vi ng ani oni c pol ymeri zati on to ATRP
(Scheme 6).
30
Usi ng thi s methodol ogy, the synthesi s of
wel l -defi ned pol y[styrene-b-di methyl si l oxane-b-(n-butyl
acryl ate)] and pol y[styrene-b-di methyl si l oxane-b-(meth-
yl methacryl ate)] tri bl ock copol ymers was accompl i shed.
These types of tri bl ock copol ymers are not accessi bl e vi a
ani oni c processes because of poor cross propagati on from
l i vi ng PDMS l i thi um si l anoate chai n ends to (meth)-
acryl ate monomers. I n the fi rst step of the bl ock
copol ymeri zati on, a l i vi ng ani oni c pol ystyrene chai n (M
n
) 4600; M
w
/M
n
) 1.09) was used to i ni ti ate the ri ng-
openi ng pol ymeri zati on of hexamethyl cycl otri si l oxane
(D
3
). Subsequent quenchi ng of the l i thi um si l anoate
chai n end of the p(Sty-b-DMS) bl ock copol ymer wi th
chl orodi methyl si l ane yi el ded a si l ane-termi nated chai n
end (M
n
) 7760; M
w
/M
n
) 1.15). A macroi ni ti ator for
ATRP was then prepared by hydrosi l ati on of the si l ane
functi onal p(Sty-b-DMS) copol ymer wi th 3-butenyl 2-bro-
moi sobutyrate. ATRP wi th the p(Sty-b-DMS) macroi ni -
ti ator wi th ei ther n-butyl acryl ate (BA) or methyl
methacryl ate (MMA) enabl ed the synthesi s of ABC
tri bl ock copol ymers. The synthesi s of these tri bl ock
copol ymers was confi rmed by si ze-excl usi on chromatog-
raphy (SEC) anal ysi s (Fi gure 2). The SEC chromato-
gram poi nted to the synthesi s of wel l -defi ned pol ymers
at each step of the bl ock copol ymeri zati on, starti ng from
pSty to p(Sty-b-DMS) ani oni cal l y, fol l owed by addi ti on
of n-butyl acryl ate (M
n
) 10 200; M
w
/M
n
) 1.18) or
methyl methacryl ate (M
n
)10 100; M
w
/M
n
)1.21) usi ng
ATRP.
Scheme 5. Synthesis of p(Sty-b-DMS-b-Sty) via
Hydrosilation and ATRP
Figure2. SEC chromatogram of ABC tri bl ock copol ymers of
p(Sty-b-DMS-b-MMA) and p(Sty-b-DMS-b-nBA) usi ng hydrosi -
l ati on and ATRP.
30
Scheme 6. Transformation of Living Anionic
Polymerization to ATRP for the Preparation of
p(Sty-b-DMS-b-MMA) and p(Sty-b-DMS-b-BA) ABC
Triblock Copolymers
Reviews Chem. Mater., Vol. 13, No. 10, 2001 3439
3.1.2. Synthesis of Graft Copolymers with
PDMS: Grafting from and Grafting through
Approaches. The synthesi s of graft copol ymers pos-
sessi ng pSty grafts and a PDMS mai n chai n was
accompl i shed by a grafti ng from approach usi ng
ATRP.
28
I n thi s method, a copol ymer of pol y(di methyl -
si l oxane-r-methyl vi nyl si l oxane) was functi onal i zed wi th
ATRP i ni ti ator groups by hydrosi l ati on wi th 4-vi nyl -
benzyl chl ori de (VBC) i n the presence of Karstedts
catal yst (i .e., pl ati num di vi nyl tetramethyl di si l oxane
compl ex, Pt(0)). The mul ti functi onal macroi ni ti ator
(M
n
) 6600; M
w
/M
n
) 1.76) was then used i n the ATRP
of Sty, yi el di ng a p(DMS-g-Sty) graft copol ymer (M
n
)
14 800; M
w
/M
n
) 2.10; Scheme 7).
Alternatively, graft copolymers with PDMS side chains
were prepared by the ATRP copol ymeri zati on of a
methacryl ate functi onal PDMS macromonomer and
methyl methacryl ate (MMA; Scheme 7).
31
Methacryl ate
PDMS macromonomers were prepared by the ani oni c
ri ng openi ng of hexamethyl cycl otri si l oxane, fol l owed by
quenchi ng of the l i thi um si l anoate chai n end wi th
[3-(methacryloxy)propyl]chlorodimethylsilane (M
n
)2200;
M
w
/M
n
)1.18). ATRP of the PDMS macromonomer wi th
MMA yi el ded a p(MMA-g-DMS) graft copol ymer (M
n
)
56 900; M
w
/M
n
) 1.97) wi th a rel ati vel y uni form di stri -
buti on of grafts throughout the copol ymer. Fi gure 3
shows the Jaacks pl ot for the ATRP copol ymeri zati on
of MMA and the PMDS macromonomer. As shown i n
the pl ot, the l ower reacti vi ty rati o of MMA usi ng ATRP
(r
MMA
) 1.24) reveal ed that a steady consumpti on of the
PDMS macromonomer occurred throughout the reac-
ti on, unl i ke i n the conventi onal radi cal process i ni ti ated
by AI BN where MMA was preferenti al l y consumed at
a faster rate (r
MMA
) 3.07).
3.2. Synthesisof ABA Triblock CopolymersCon-
taining Polysilylenes. Pol ymers contai ni ng substi -
tuted pol ysi l yl enes (pol ysi l anes) are of i nterest for
appl i cati ons as photoresi st, photoconducti ng, and non-
l i near opti cal materi al s. The i nteresti ng el ectroni c and
opti cal properti es of these materi al s ari se from the
del ocal i zati on of l ow-l yi ng el ectrons i n the Si -Si
backbone of the pol ymer.
32
I n an effort to i mprove the
mechani cal properti es and processi ng of these materi al s,
bl ock copol ymers wi th pSty segments were i ncorporated
i nto pol ysi l anes usi ng ATRP.
33
I n thi s approach, pol y-
(methyl phenyl si l ane) (PMPS) was prepared by the
Wurtz-type reducti ve coupl i ng of di chl oromethyl phe-
nyl si l ane i n the presence of sodi um and was end-capped
wi th a (Scheme 8). ATRP of Sty from the di functi onal
benzyl chl ori de macroi ni ti ator (M
n
)4550; M
w
/M
n
)5.9)
yi el ded an ABA tri bl ock copol ymer of p(Sty-b-MPS-b-
Sty) (M
n
) 46 550; M
w
/M
n
) 10.6).
3.3. Hybrid Polymers Containing Polyhedral
Oligomeric Silsesquioxanes (POSS). Pol ymers con-
tai ni ng si de-chai n groups of POSS
34
represent a novel
cl ass of hybri ds that i s anti ci pated to i mpart greater
thermal and mechani cal stabi l i ty to a materi al .
35-38
These i norgani c groups can be i ncorporated i nto pol ymer
chai ns vi a CRP of a POSS contai ni ng monomer (e.g.,
methacryl ate and styrene) or i ni ti ated from a POSS
contai ni ng al kyl hal i de (e.g., benzyl chl ori de). Structur-
al l y, T8-POSS monomers are cubi c si l oxane octamers
and have an outer di ameter of 1.5 nm.
34
I t i s the
i ncl usi on of these bul ky i norgani c pendant groups that
gi ves POSS pol ymers thei r unusual structure and
properti es. Whi l e POSS pol ymers and materi al s have
been prepared from a vari ety of methods, the appl i cati on
of POSS monomers to CRP al l owed for greater control
of pol ymer mol ecul ar wei ght, topol ogy, and composi ti on.
Recentl y, a methacryl ate-contai ni ng POSS compound,
3-(3,5,7,9,11,13,15-heptacycl opentyl pentacycl o[9.5.1.
1.
3,9
1.
5,15
1
7,13
]octasi l oxane-1-yl )propyl methacryl ate (MA-
POSS) was pol ymeri zed by ATRP to prepare homopol y-
mers, ABA tri bl ock and AB star di bl ock copol ymers
(Scheme 9).
39
ATRP of MA-POSS i n the presence of
ethyl 2-bromoi sobutyrate (Scheme 9) yi el ded homopol y-
Figure3. Jaacks pl ots for the copol ymeri zati ons of MMA wi th
PDMS macromonomer (Mn ) 2200, 5 mol % i n the feed) i n a
xyl ene sol uti on (MMA/xyl ene ) 1/1 by wei ght) usi ng the
conventi onal radi cal pol ymeri zati on (RP) and ATRP. Condi -
ti ons: RP, [MMA]0/[macromonomer]0/[AI BN]0 ) 380/20/1, 75
C; ATRP, [MMA]0/[macromonomer]0/[i ni ti ator]0/[CuCl ]0/[dn-
Nbpy]0 ) 285/15/1/1/2, 90 C (dnNbpy ) 4,4-di nonyl -2,2-
bi pyri di ne).
31
Scheme 7. Synthesis of p(DMS-g-Sty) and
p(MMA-g-DMS) Graft Copolymers Using ATRP
Scheme 8. Synthesis of p(Sty-b-MPS-b-Sty) ABA
Triblock Copolymers
3440 Chem. Mater., Vol. 13, No. 10, 2001 Reviews
mers of p(MA-POSS). ABA tri bl ock copol ymers were
synthesi zed by the ATRP of MA-POSS from a di func-
ti onal pol y(n-butyl acryl ate) (pBA) macroi ni ti ator (M
n,SEC
) 13 750; M
w
/M
n
) 1.17). SEC of the p[(MA-POSS)-b-
(BA)-b-(MA-POSS)] copol ymer (M
n,SEC
) 22 800; M
w
/M
n
) 1.19, Fi gure 4) and
1
H NMR confi rmed successful
chai n extensi on of MA-POSS from the macroi ni ti ator.
To prepare copol ymers wi th more compl ex archi tectures,
a three-armed pol y(methyl acryl ate) (pMA) star pol ymer
(M
n,SEC
) 7390; M
w
/M
n
) 1.08) was used as a macro-
i ni ti ator i n the ATRP of MA-POSS, yi el di ng a wel l -
defi ned AB star di bl ock copol ymer of p[MA-b-(MA-
POSS)] (M
n,SEC
) 18 060; M
w
/M
n
) 1.30).
Hybri d pol ymers have al so been prepared by usi ng
monofuncti onal POSS i ni ti ators i n the ATRP of Sty
(Scheme 9).
40
I n the pol ymeri zati on, a POSS i ni ti ator
beari ng one benzyl chl ori de and seven cycl opentyl
groups at the corners of the cycl i c si l sesqui oxane was
used, yi el di ng a wel l -defi ned pSty homopol ymer wi th a
POSS end group. Usi ng condi ti ons si mi l ar to those
previ ousl y reported, compari son of the monomer conver-
si on and mol ar mass evol uti on wi th monomer conver-
si on (Fi gure 5) reveal ed that the presence of a bul ky
si l sesqui oxane group di d not affect the i ni ti ati ng capa-
bi l i ty of the benzyl chl ori de moi ety. Addi ti onal l y, pSty
wi th POSS end groups made from ATRP possessed
rel ati vel y l ow pol ydi spersi ty (M
w
/M
n
) 1.24).
4. Hybrid Star Polymers fromInorganic
Initiators
Organi c star pol ymers wi th i norgani c cores compri se
another cl ass of hybri d materi al . An advantage of usi ng
i norgani c i ni ti ators to prepare stars from a core-fi rst
approach i s the abi l i ty to make mul ti functi onal i ni ti a-
tors wi th preci se functi onal i ty and reacti vi ty. Addi ti on-
al l y, wel l -defi ned star pol ymers of hi gher mol ecul ar
wei ght (M
n
> 500 000) have been synthesi zed because
of the i ncorporati on of mul ti pl e i ni ti ati on si tes to a
si ngl e mol ecul e.
4.1Cyclophosphazeneand Cyclotetrasiloxanes
as Multifunctional Initiators for ATRP. The syn-
Scheme 9. Synthesis of POSS Containing Hybrid Polymers Using ATRP
Reviews Chem. Mater., Vol. 13, No. 10, 2001 3441
thesi s of star (co)pol ymers from mul ti functi onal phos-
phazenes and si l oxanes was conducted. The preparati on
of these mul ti functi onal i ni ti ators enabl ed the synthesi s
of wel l -defi ned homopol ymers and bl ock (co)pol ymers
usi ng ATRP.
41
Hexafuncti onal i norgani c i ni ti ators were
synthesi zed by the transformati on of hydroxy groups
from 1,1,3,3,5,5-hexaki s[4-(hydroxymethyl )phenoxy]cy-
cl otri phosphazene to benzyl i c hal i des, or R-hal oesters.
From thi s route, hexafuncti onal i norgani c i ni ti ators
beari ng benzyl bromi de, 2-bromopropri onate, or 2-bro-
moi sobutyrate groups were prepared. The use of these
i ni ti ators enabl ed the synthesi s of hi gh mol ar mass/l ow
pol ydi spersi ty pMA star pol ymers (M
n
) 557 000; M
w
/
M
n
) 1.19) and star di bl ock copol ymers of pol y(methyl
acryl ate-b-i sobornyl acryl ate) (M
n
) 48 000; M
w
/M
n
)
1.37) usi ng ATRP. Tetrafuncti onal i ni ti ators for ATRP
were al so prepared by the hydrosi l ati on of 1,3,5,7-
tetramethyl cycl otetrasi l oxane and VBC. Thi s tetrafunc-
ti onal i ni ti ator was used i n the synthesi s of a pSty star
pol ymer (M
n
) 12 600; M
w
/M
n
) 1.11) usi ng ATRP.
4.2. Metalloinitiatorsin theSynthesisof Hybrid
Polymers. The synthesi s of transi ti on-metal -contai ni ng
pol ymers i s an area of i nterest for appl i cati ons as
sensors
42
and l umi nescent materi al s.
43
An el egant
synthesi s to prepare hybri d star pol ymers possessi ng a
transi ti on-metal core and organi c pol ymer arms has
been conducted usi ng ATRP.
44-49
These metal l oi ni ti a-
tors were compri sed of transi ti on-metal compl exes pos-
sessi ng i ni ti ati ng si tes for ATRP and were prepared by
coordi nati on of functi onal bi pyri di ne l i gands to ruthe-
ni um(I I ) sal ts. Functi onal bi pyri di ne l i gands possessi ng
ei ther benzyl chl ori de or 2-bromoi sobutyrate groups
were synthesi zed, enabl i ng the effi ci ent i ni ti ati on of
styrenes and (meth)acryl ates (Scheme 10). I n these
systems, hexafuncti onal , tetrafuncti onal , and di func-
ti onal i ni ti ators were made by varyi ng the stoi chi omet-
ri c rati os of functi onal bpy l i gands to the rutheni um(I I )
core. Subsequent appl i cati on of these metal l oi ni ti ators
resul ted i n wel l -defi ned l i near, four-armed and si x-
armed star pol ymers of pSty (M
n,si x-armed star
) 139 000;
M
w
/M
n
)1.24) and pMMA (M
n,si x-armed star
)54 000; M
w
/
M
n
) 1.07; Fi gure 6). Cl eavage of pMMA chai ns from
the si x-armed pMMA star pol ymer reveal ed that wel l -
defi ned pol ymers were obtai ned (M
n
) 8060; M
w
/M
n
)
1.13; Fi gure 6) wi th mol ar masses i n rel ati vel y good
agreement wi th theoreti cal val ues (M
n,theoreti cal
)6900).
48
5. Organic/Inorganic Hybrid Nanoparticles
Hybri d materi al s composed of i norgani c nanoparti cl es
and organi c surface groups possess i nteresti ng opti cal ,
50
magneti c,
51
and bl endi ng
52
properti es. These hybri ds
contai ni ng nanoparti cl es have been prepared by other
syntheti c routes by trappi ng col l oi ds wi thi n cross-l i nked
Figure4. SEC chromatogram of p[(MA-POSS)-b-BA-b-(MA-
POSS)] tri bl ock copol ymer prepared usi ng ATRP.
39
Figure5. Pl ot of mol ar mass (fi l l ed ci rcl es) and pol ydi spersi ty
(squares) vs monomer conversi on i n the ATRP of Sty wi th the
fol l owi ng condi ti ons: [monomer]/[i ni ti ator]/[Cu
I
Cl ]/[PMDETA]
) 8.6 M/0.089 M/0.045 M/0.045 M at 120 C (PMDETA )
N,N,N,N,N-pentamethyl di ethyl enetri ami ne).
Figure6. SEC chromatogram of a si x-armed pMMA star (Mn
) 54 000; Mw/Mn ) 1.07) and cl eaved pMMA arms (Mn ) 8060;
Mw/Mn ) 1.13).
48
Scheme 10. Multifunctional Metalloinitiators for
ATRP fromRuthenium(II) Complexes
3442 Chem. Mater., Vol. 13, No. 10, 2001 Reviews
matri xes,
53
grafti ng to parti cl es wi th functi onal mol -
ecul es/pol ymers,
25
or grafti ng from parti cl es usi ng a
l i vi ng or control l ed pol ymeri zati on process.
54
Control l ed
radi cal pol ymeri zati on techni ques have al so been i n-
troduced to col l oi dal materi al s by the attachment of
ATRP i ni ti ati ng groups to the parti cl e surface. Subse-
quent ATRP of vi nyl monomers yi el ded core-shel l
parti cl es wi th wel l -defi ned homopol ymers and bl ock
copol ymers tethered to a col l oi dal i ni ti ator.
55,56
The
properti es of hybri d nanoparti cl es prepared from thi s
method can be tuned by varyi ng the parti cl e si ze of the
col l oi dal i ni ti ator, changi ng the composi ti on of the
parti cl e core, or tetheri ng (co)pol ymers wi th novel
composi ti on/functi onal i ty. An i nteresti ng feature of
hybri d nanoparti cl e ul trathi n fi l ms has been the forma-
ti on of ordered two-di mensi onal arrays of parti cl es, wi th
a spaci ng dependent on the radi us of gyrati on of the
tethered (co)pol ymer. The general methodol gy for the
synthesi s of hybri d nanoparti cl es from ATRP i s pre-
sented i n Scheme 11.
Si l oxane-based nanoparti cl es have been successful l y
appl i ed to ATRP systems to prepare wel l -defi ned hybri d
nanoparti cl es. I n the fi rst step of the process, nanopar-
ti cl es were synthesi zed vi a the base-catal yzed hydrol ysi s
and condensati on of tetral koxysi l anes (i .e., the Stober
process)
57,58
or by mi croemul si on pol ymeri zati on of
tri al koxysi l anes.
59
Condensati on reacti ons of surface
si l anol groups wi th functi onal si l anes yi el ded col l oi dal
i ni ti ators beari ng benzyl chl ori de, 2-bromopropi onate,
or 2-bromi sobutyrate groups. The synthesi s of hybri d
nanoparti cl es was then conducted by usi ng the col l oi dal
i ni ti ators i n the ATRP of vari ous vi nyl monomers.
5.1. Hybrid Nanoparticles fromSilica Colloids.
A modi fi cati on of the Stober process was devel oped to
prepare si l i ca (Si O
2
) col l oi dal i ni ti ators for ATRP.
55
Dynami c l i ght scatteri ng (DLS) and transmi ssi on el ec-
tron mi croscopy (TEM) reveal ed that functi onal si l i ca
parti cl es wi th an average effecti ve di ameter (D
eff
) of 70
nm were obtai ned. Si l i ca col l oi ds wi th benzyl chl ori de
groups on the surface were used i n the ATRP of Sty.
DLS and TEM confi rmed that D
eff
of the pSty hybri d
nanoparti cl es i ncreased wi th monomer conversi on. SEC
of pSty chai ns cl eaved from the parti cl e confi rmed the
synthesi s of wel l -defi ned pol ymers of l ow pol ydi spersi ty
(M
w
/M
n
< 1.35) and havi ng M
n
) 26 500 i n cl ose
agreement wi th M
n,theoreti cal
) 30 600 val ues. Thi s evi -
dence supported the control l ed growth of pSty from the
parti cl e surface. TEM i mages of pSty nanoparti cl e
ul trathi n fi l ms reveal ed the presence of hexagonal
packi ng of col l oi ds i n a pol ymer matri x (Fi gure 7). The
rel ati ve uni formi ty of parti cl e si zes, as wel l as the
regul ari ty i n the i nterparti cl e spaci ng, al so poi nted to
the successful synthesi s of both wel l -defi ned col l oi ds and
tethered pol ymers.
The composi ti ons of the col l oi dal i ni ti ators were al so
modi fi ed to encapsul ate cadmi um sul fi de parti cl es i n a
shel l of si l i ca.
60
ATRP i ni ti ati ng groups were i ntroduced
to the si l i ca surface by the condensati on of functi onal
monoalkoxysilanes containing 2-bromopropionate groups.
The ATRP of Sty from these core-shel l col l oi dal i ni ti a-
tors yi el ded an array of l umi nescent parti cl es i n a
matri x of tethered pSty.
5.2. Block Copolymer HybridNanoparticlesfrom
PolysilsesquioxaneNanoparticles. The synthesi s of
pol ysi l sesqui oxane col l oi dal i ni ti ators for ATRP was
conducted by the mi croemul si on pol ymeri zati on of tri -
al koxysi l anes.
56
The resul ti ng spheri cal networks were
not si l i ca (Si O
2
) but were pol ysi l sesqui oxane (Si O
1.5
).
Surface treatment of si l anol groups wi th functi onal
chl orosi l anes possessi ng 2-bromoi sobutyrate groups, i n
addi ti on to other si l yl ati ng agents, yi el ded di screte
col l oi ds wi th ATRP i ni ti ati ng moi eti es. DLS and atomi c
force mi croscopy (AFM) both reveal ed that rel ati vel y
uni form parti cl es were synthesi zed (D
eff,DLS
)27 nm and
D
eff,AFM
) 19 nm). The ATRP of Sty and benzyl acryl ate
(BzA) was then conducted to prepare hybri d nanopar-
ti cl es wi th tethered bl ock copol ymers. SEC of the
cl eaved pSty (M
n
) 5250; M
w
/M
n
) 1.22) and p(Sty-b-
BzA) (M
n
) 27 280; M
w
/M
n
) 1.48) confi rmed that the
successi ve ATRP of Sty and BzA from parti cl es was
successful . The resul ti ng hybri d nanoparti cl es from
pol ysi l sesqui oxane col l oi ds possessed vol ume/wei ght
fracti ons of tethered pol ymer exceedi ng that of the
i norgani c core. AFM tappi ng mode observati ons of the
Scheme 11. Synthesis of Hybrid Nanoparticles
Using ATRP
Figure7. TEM of a hybri d pSty nanoparti cl e wi th Deff ) 79
nm of a Si O2 col l oi dal i ni ti ator (si ze bar ) 100 nm).
55
Reviews Chem. Mater., Vol. 13, No. 10, 2001 3443
(sub)monol ayers of the p(Sty-b-BzA) hybri d nanopar-
ti cl es reveal ed the di rect resul t of tethered copol ymer
composi ti on on the morphol ogy of the materi al on mi ca.
I n parti cul ar, AFM phase-contrast i mages showed that
each component of the hybri d nanoparti cl e was di scern-
i bl e i n ul trathi n fi l ms cast onto mi ca (Fi gure 8). These
i mages i mpl i ed that hard cores (col l oi dal i ni ti ators) were
surrounded by a hard corona (tethered pSty segment)
and di spersed wi thi n a soft conti nuous matri x (tethered
pBzA segment).
5.3. Organic/Inorganic Materials from Micron-
Sized Inorganic Particles. The attachment of wel l -
defi ned pol ymers to l arge parti cl es (D
eff
> 1 m) has
been conducted usi ng CRP. Previ ousl y, surface-i ni ti ated
pol ymeri zati ons from mi cron-si zed parti cl es had been
conducted using conventional radical polymerization.
61-64
However, by the use of CRP from parti cl es, pol ymer
coati ngs of control l ed thi ckness and functi onal i ty were
prepared. I n parti cul ar, hybri ds from l arger parti cl es
were synthesi zed as potenti al chromatographi c stati on-
ary phases
65-68
and templ ated supports.
69
I n the prepa-
rati on of stati onary phases for l i qui d chromatography,
thi n fi l ms (100 ) of pol y(acryl ami de) were grown from
benzyl chl ori de functi onal porous si l i ca parti cl es (D
eff
) 5 m and pore si ze
ave
) 860 ) usi ng ATRP. The
successful separati on of vari ous protei ns usi ng these
pol y(acryl ami de) parti cl es poi nted to the successful
grafti ng of pol ymers, wi thout si gni fi cant cl oggi ng of
parti cl e pores.
65
Si mi l arl y, pol y(methacryl ates) possess-
i ng nucl eoti de si de-chai n groups were grown from
porous si l i ca parti cl es usi ng ATRP. The i mmobi l i zati on
of ol i gonucl eoti des has been demonstrated as an attrac-
ti ve approach for the templ ated synthesi s of nucl ei c
aci ds, wi th the pri mary goal bei ng control of both the
degree of pol ymeri zati on and sequence di stri buti on i n
the fi nal product. Toward thi s endeavor, methacryl ate
deri vati ves of uri di ne and adenosi ne were synthesi zed
and pol ymeri zed usi ng a 2-bromoi sobutyrate functi onal
si l i ca parti cl e.
69
I n a di fferent templ ated system, pol y-
(benzyl methacryl ate) was grafted to a si l i ca surface
usi ng ATRP and treated wi th hydrofl uori c aci d to
prepare hol l ow pol ymeri c col l oi ds.
70
Hybri d parti cl es
wi th tethered pSty were al so prepared usi ng ATRP from
2-chl oro-2-phenyl acetate functi onal si l i ca parti cl es.
71
6. Dispersed Silicate Nanocomposites
The synthesi s of di spersed si l i cate nanocomposi tes
was conducted by the CRP of Sty wi thi n l ayers of
al koxyami ne-l oaded montmori l l oni te (Scheme 12).
72
Organi c/i norgani c nanocomposi tes of i ntercal ated and
del ami nated si l i cates contai ni ng pol ymers i s an area of
conti nued i nterest owi ng to the enhanced thermal and
di mensi onal stabi l i ty these materi al s possess. Whi l e a
vari ety of techni ques have been devel oped for the
synthesi s of pol ymer l ayered si l i cate nanocomposi tes,
the preparati on of di spersed si l i cate nanocomposi tes
was not as extensi vel y devel oped.
73
However, by the use
of control l ed radi cal pol ymeri zati on, di spersi ons of cl ay
parti cl es wi thi n a matri x of wel l -defi ned pSty were
formed. By the synthesi s of an al koxyami ne wi th a
pendant quaternary ammoni um group, sodi um cati ons
were exchanged from the pri sti ne cl ay, al l owi ng for
l oadi ng of SFRP i ni ti ators between the si l i cate l ayers.
X-ray di ffracti on (XRD) patterns provi ded evi dence for
the l oadi ng and i ntercal ati on of al koxyami nes between
si l i cate l ayers by the i ncrease i n the i nterl ayer di stance
from d ) 1.26 nm (Na
+
spaci ng) to d ) 2.35 nm
(al koxyami ne spaci ng; Fi gure 9a,b). Subsequent addi -
ti on and pol ymeri zati on of Sty at 125 C i n the presence
of the functi onal montmori l l oni te resul ted i n compl ete
del ami nati on of the si l i cate l ayers. XRD provi ded fur-
ther evi dence for the del ami nati on and di spersal of
si l i cates by the di sappearance of the di ffracti on pattern
after the SFRP of Sty (Fi gure 9c). I on exchange and
extracti on of p(Sty) (M
n
) 21 500; M
w
/M
n
) 1.3) from
the di spersed nanocomposi te reveal ed that wel l -defi ned
pol ymers were made, wi th M
n
val ues i n cl ose agreement
wi th theoreti cal predi cti ons.
7. Polymer Brushes and Modified Flat Surfaces
The use of CRP techni ques to prepare wel l -defi ned
tethered (co)pol ymers has been demonstrated to be an
effecti ve approach toward modi fyi ng surfaces wi th
potenti al appl i cati ons i n mi croel ectroni cs and nanoscal e
patterni ng.
74,75
Whi l e other pol ymeri zati on methods
have been uti l i zed to prepare these pol ymer brushes,
76,77
CRP methods al l ow the i ntroducti on of a broader range
of functi onal i ty (e.g., aci d, perfl uori nated) to modi fy
surfaces i n a more versati l e fashi on usi ng l ess stri ngent
reacti on condi ti ons. A number of CRP techni ques have
Figure8. AFM phase i mage of a p(Sty-b-BzA) hybri d nano-
parti cl e (sub)monol ayer on mi ca. Assi gnment of domai ns i s as
fol l ows: dark spots (pol ysi l sesqui oxane parti cl es); dark corona
around parti cl es (tethered pSty; Mn ) 5250; Mw/Mn ) 1.22);
l i ght conti nuous matri x [tethered p(Sty-b-BzA); Mn ) 27,280;
Mw/Mn ) 1.48].
56
Scheme 12. Synthesis of Dispersed Silicate
Nanocomposites fromSFRP of Styrene within
Montmorillonite
3444 Chem. Mater., Vol. 13, No. 10, 2001 Reviews
been used successful l y to make pol ymer brushes from
si l i con and gol d substrates, namel y, SFRP,
78-80
ATRP,
78,81-93
and RAFT.
94
The general procedure to prepare pol ymer brushes
requi res the attachment of an i ni ti ator mol ecul e to the
fl at substrate fol l owed by CRP of a vi nyl monomer from
the surface (Scheme 13). To functi onal i ze Si wafers,
chl orosi l anes beari ng al koxyami nes, R-hal oesters, di thi o-
carbamates, or azo compounds were used to coval entl y
bi nd to si l anol groups ari si ng from the thi n oxi di zed
l ayer of Si O
2
on the wafer. Synthesi s of i ni ti ator-
functi onal i zed Au surfaces for ATRP was conducted by
the sel f-assembl y of a 11-mercaptoundecanol fol l owed
by esteri fi cati on of the al cohol wi th an aci d bromi de
contai ni ng an i ni tati ng moi ety.
7.1. Methodsfor ControlledGrowth of Tethered
PolymersfromSurfacesUsingCRP. CRP reacti ons
from surfaces as depi cted i n Scheme 13 are compl i cated
by the extremel y l ow concentrati on of i ni ti ati ng si tes
on the surface. Thi s probl em i s al so compounded by the
very smal l concentrati on of persi stent radi cal (deacti va-
tor) that i s generated upon acti vati on of the i ni ti ator.
Thus, rapi d i ni ti ati on and propagati on of the growi ng
tethered chai n may occur vi a a redox process, resul ti ng
i n an uncontrol l ed pol ymeri zati on. The key to overcom-
i ng thi s probl em i s the generati on or addi ti on of a
suffi ci ent amount of persi stent radi cal (deacti vator) i n
the earl y stages of the pol ymeri zati on to ensure con-
trol l ed growth of pol ymers from fl at substrates. Two
general approaches have been reported to prepare wel l -
defi ned pol ymer brushes and are di scussed i n the
fol l owi ng secti ons.
7.1.1. Addition of Sacrificial Initiator. I n thi s
system, untethered i ni ti ator was added to a CRP
reacti on from a surface. The SFRP of Sty from a Si
surface (Scheme 13) has been extensi vel y i nvesti gated
to demonstrate thi s concept.
78
The addi ti on of unteth-
ered i ni ti ator [free al koxyami ne and 1-phenyl -1-(22,66-
tetramethyl-1-piperidinyloxyethane)] performed the dual
purpose of i ncreasi ng the rate of the pol ymeri zati on,
whi l e al l owi ng for control l ed growth of tethered pSty.
The external addi ti on of untethered i ni ti ator served to
generate a suffi ci ent concentrati on of persi stent radi cal
(TEMPO) to establ i sh the CRP equi l i bri um. Thus, by
the termi nati on of untethered radi cal s i n sol uti on, a
hi gher concentrati on of persi stent radi cal (TEMPO) i n
the system was formed, shi fti ng the equi l i bri um to the
dormant speci es. Consequentl y, the thi ckness of the
tethered pol ymer fi l ms i ncreased l i nearl y wi th the mol ar
mass (M
n
) of the untethered pol ymer, i ndi cati ng that
control l ed pol ymeri zati on from the surface was success-
ful (Fi gure 10). Because the pol ymer brush hei ght was
l ess than the ful l y extended contour l ength of the
unbound pSty, i t can be i nferred that some col l apse of
the tethered pol ymer chai ns occurred on the surface.
7.1.2. External Addition of Persistent Radical/
Deactivator. An al ternati ve approach to control l i ng
radi cal pol ymeri zati ons from surfaces was the addi ti on
of persi stent radi cal (deacti vator) at the begi nni ng of a
CRP reacti on. I n CRP systems conformi ng to the PRE
model , the generati on of persi stent radi cal (deacti vator)
i s generated i n si tu after a suffi ci ent bui l dup of termi -
nated products.
8
However, by the external addi ti on of
persi stent radi cal at the i ni ti al stages of the pol ymer-
i zati on, radi cal s from the surface were deacti vated,
enabl i ng conti nued exchange reacti ons and control l ed
growth of tethered pol ymers. External addi ti on of
deacti vator was i l l ustrated i n the ATRP of styrene and
acryl ates from Si wafers, by the use of Cu(I I ) deacti vat-
i ng compl exes at the begi nni ng of the reacti on.
82
I n
ATRP reacti ons of Sty wi thout addi ti on of Cu(I I ) at the
begi nni ng, uncontrol l ed growth of tethered pSty oc-
curred wi th a fi l m thi ckness of 106 ( 5 nm. However,
by addi ng Cu(I I ), a control l ed pol ymeri zati on occurred,
as evi denced by a l i near rel ati onshi p of pSty pol ymer
Figure 9. XRD pattern of (a) untreated montmori l l onate,
i nterl ayer spaci ng ) 1.26 nm, (b) al koxyami ne-l oaded si l i cate,
i nterl ayer spaci ng ) 2.35 nm, and (c) PSty-si l i cate-di spersed
nanocomposi te (Mn,pSty ) 21 500; Mw/Mn ) 1.3).
72
Scheme 13. Synthesis of Polymer Brushes fromSi
and Au Surfaces Using CRP
Figure 10. Li near dependence of a pol ymer brush wi th a
tethered pSty brush thi ckness wi th a mol ar mass of untethered
pSty.
78
Reviews Chem. Mater., Vol. 13, No. 10, 2001 3445
brush thi ckness wi th predi cted mol ar mass (M
n
) of
tethered pSty.
7.2. Control of SurfaceProperties and Pattern-
ingon CRP-Prepared Polymer Brushes. Modi fi ca-
ti on of tethered pol ymer composi ti on has been demon-
strated to effect both surface properti es and wettabi l i ty
of vari ous substrates. Pol ymer brushes wi th tethered
random copol ymers of p(Sty-r-MMA) and p[Sty-r-(hy-
droxyethyl methacryl ate) (HEMA)] have been prepared
from both grafti ng to
74
and grafti ng from
78
ap-
proaches usi ng SFRP. I n both systems, the i ncorpora-
ti on of wel l -defi ned random copol ymers had a profound
effect on the wetti ng behavi or of the pol ymer brushes.
The surface properti es of Si wafers have al so been
modi fi ed by the i ncorporati on of wel l -defi ned hydropho-
bi c and hydrophi l i c pol ymer segments usi ng ATRP. By
the homopol ymeri zati on of a perfl uori nated monomer
(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafl uorode-
cyl acryl ate), a pol ymer brush wi th a hydrophobi c
surface was prepared, as evi denced by water contact
angl e measurements (119 ( 2). Hydrophi l i c Si surfaces
were made by the control l ed growth of a pol y[styrene-
b-(tert-butyl acryl ate)] [p(Sty-b-tBA)] fol l owed by hy-
drol ysi s to yi el d the correspondi ng pol y(styrene-b-acryl i c
aci d) [p(Sty-b-AA)] pol ymer brush. Contact angl e mea-
surements from water dropl ets i ndi cated a decrease i n
the contact angl e goi ng from p(Sty-b-tBA) (86 ( 4) to
p(Sty-b-AA) (18 ( 2) surfaces.
Control of nanoscal e morphol ogy of p(Sty-b-MMA)
pol ymer brushes has been demonstrated by treatment
of surfaces wi th sel ecti ve organi c sol vents.
86
Pol ymer
brushes of p(Sty-b-MMA) were synthesi zed by a com-
bi nati on of cati oni c pol ymeri zati ons of Sty, fol l owed by
the ATRP of MMA.
83
I mmersi on of the p(Sty-b-MMA)
modi fi ed wafer i n CH
2
Cl
2
and dryi ng under a stream of
ai r yi el ded pol ymer brushes wi th smeared features and
rel ati vel y smooth surfaces. Thi s morphol ogy i s pre-
sumed to ari se from a more extended conformati on of
the tethered copol ymer, because CH
2
Cl
2
i s a good
sol vent for both segments (Fi gure 11a). Treatment of
thi s pol ymer brush i n cycl ohexane resul ted i n an i r-
regul ar worml i ke morphol ogy due to preferenti al swel l -
i ng of the pSty segment. Fi nal l y, i mmersi on of the brush
wi th CH
2
Cl
2
and mi xed sol vent sol uti ons of CH
2
Cl
2
/
Figure11. AFM i mage of p(Sty-b-MMA) pol ymer brushes wi th pSty thi ckness ) 23 nm and pMMA thi ckness ) 14 nm: (a) after
i mmersi on i n CH2Cl 2 for 30 mi n and dryi ng under a stream of ai r; (b) after i mmersi on i n CH2Cl 2 and CH2Cl 2/cycl ohexane sol uti ons
and dryi ng under a stream of ai r.
86
Figure12. (a) Opti cal mi crograph of a 10 m patterned pol ymer brush wi th regi ons of pol y(tBA) (dark) and pol y(AA) (l i ght). (b)
Opti cal mi crograph of a 200 m pattern pol ymer brush wi th water dropl et wetti ng pol y(AA) domai ns.
80
3446 Chem. Mater., Vol. 13, No. 10, 2001 Reviews
cycl ohexane yi el ded an el l i psoi dal array of tethered
copol ymers (Fi gure 11b), presumabl y from the col l apse
and encapsul ati on of pMMA wi thi n the tethered pSty
segment.
Patterni ng of pol ymer brushes on a mi cron scal e was
achi eved through the use of an aci d-generati ng photo-
resi st.
80
I n thi s system, tethered pol ymers of p(t-BA)
were prepared by SFRP usi ng R-hydrogen-contai ni ng
ni troxi des
12
and the compl ementary tethered al koxy-
ami nes. Spi n coati ng of the photoresi st mi xture on the
pol ymer brush, fol l owed by radi ati on through a mask,
yi el ded ordered patterns wi th 10 m
2
domai ns of pSty
and pAA (Fi gure 12a). As expected, the presence of these
di screte domai ns had a tremendous effect on the wetti ng
behavi or of the surface. Opti cal mi crographs of a water
dropl et on a 200 m patterned surface reveal ed the
sel ecti ve wetti ng of the pAA regi ons as defi ned by the
si ze of the pattern (Fi gure 12b).
8. Nanoporous Inorganic Networks Templated
from(Co)polymers Prepared fromCRP
Pol ymeri c shape templ ates made from CRP were used
i n the preparati on of nanoporous pol ysi l sesqui oxane
networks. Nanoporous i norgani c networks were tar-
geted to obtai n materi al s of l ower di el ectri c constant
rel ati ve to conventi onal si l i cate materi al s. Nanoporous
pol ysi l sesqui oxanes were made by pol ymeri zati on of
methyl si l sesqui oxane resi ns i n the presence of p(MMA-
r-HEMA) star copol ymers, fol l owed by thermal degrada-
ti on of the pol ymeri c templ ate.
95
Star copol ymers of
MMA and HEMA were made usi ng ATRP from mul ti -
armed dendri ti c i ni ti ators. I t was found that star
copol ymers contai ni ng pol ar substi tuents were requi red
to avoi d macroscopi c phase separati on of the pol ymer
and the i norgani c network upon cure. I n general , star
copol ymers of p(MMA-r-HEMA) were kept to l ow mol ar
mass (M
n
< 8000) and pHEMA composi ti ons to around
20 mol %. By the use of a si x-armed star of p(MMA-
HEMA) (12-mol % pHEMA; M
n,SEC
) 5000; M
w
/M
n
)
1.27), nanoporous pol ysi l sesqui oxane networks ( ) 2.2)
of l ower di el ectri c constant rel ati ve to the densi fi ed
network ( ) 2.8) were obtai ned.
9. Conclusion/Future Perspectives
The synthesi s of hybri d organi c/i norgani c nanocom-
posi tes offers a route to new materi al s wi th predefi ned
structure and performance. The use of CRP methodol o-
gi es opens the door to a host of wel l -defi ned organi c
pol ymers whi ch can be i ncorporated to many di fferent
i norgani c substrates. The attachment of organi c pol y-
mers to i norgani c pol ymers, parti cl es, surfaces, and
networks has been conducted usi ng CRP techni ques and
has demonstrated the versati l i ty of thi s approach. Whi l e
thi s semi nal work has proven successful , vari ati ons and
combi nati ons of these methods wi l l need to be expl ored
to prepare trul y advanced materi al s possessi ng a novel
synergi sm of properti es. Future devel opments i n thi s
fi el d may i ncl ude synthesi s of novel hybri d nanocom-
posi tes, i ncl udi ng i nterpenetrati ng pol ymer networks,
nano-objects, and bi omi meti c materi al s. An obvi ous, but
promi si ng, di recti on i n thi s fi el d wi l l al so be to use CRP
to prepare the pol ymeri c components i n organi c/i nor-
gani c nanocomposi tes that previ ousl y requi red i oni c
pol ymeri zati on processes.
Acknowledgment. Dr. Peter Mi l l er, Hosei Shi noda,
Dr. Yoshi ki Nakagawa, Dr. Tomasz Kowal ewski , Dr.
Gary Patterson, Dani el Savi n, and Dr. Gui do Ki ckel bi ck
are grateful l y acknowl edged for contri buti ons to thi s
revi ew. We al so thank the Nati onal Sci ence Foundati on
(DMR 9871450) and the Atom Transfer Radi cal Pol ym-
eri zati on Consorti um and the Control l ed Radi cal Po-
l ymeri zati on Consorti um at CMU for fundi ng of thi s
research.
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