518 Biomacromolecules 2001, 2, 518-525

Modification of Natural and Artificial Polymer Colloids by

“Topology-Controlled” Emulsion Polymerization
David J. Lamb, James F. Anstey, Christopher M. Fellows, Michael J. Monteiro,† and
Robert G. Gilbert*
Key Centre for Polymer ColloidssF11, School of Chemistry, University of Sydney,
Sydney, New South Wales 2006, Australia
Received December 26, 2000; Revised Manuscript Received March 27, 2001

A diffuse layer of water-soluble polymer chemically grafted to the surface of a hydrophobic polymer colloid
has been created by the second-stage polymerization of dimethylaminoethyl methacrylate (DMAEMA) onto
the biomacromolecule polyisoprene in natural rubber latex and also onto synthetic polybutadiene and
polystyrene latexes. To control the locus of radical formation, the process was initiated by a redox couple
wherein one component (e.g., cumene hydroperoxide) is hydrophobic and the other (e.g., tetraethylenepent-
amine) is hydrophilic. The modified latexes displayed a dramatic increase in colloidal stability at low pH
which is attributed to grafted hydrophilic polymer acting as an electrosteric stabilizer; the effect is particularly
remarkable in natural rubber latex, which usually has poor colloidal stability for pH j 8. 13C NMR was
performed to verify the existence of the grafted copolymer and to quantify yield. The mechanism by which
such a novel morphology can be generated is postulated to be via a process of radical formation at the
particle surface followed by the subsequent grafting to the hydrophobic polymer backbone and polymerization
of hydrophilic monomer in the aqueous phase. This technique is potentially useful for creating novel materials
from natural rubber latex.

I. Introduction to yield a synthetically modified latex, and indeed there are

The design of novel copolymers with specific and con-
trolled molecular architectures is both an intellectual chal-
lenge (equivalent to the synthesis of unusual molecules by
organic chemists) and a procedure with considerable techni-
cal potential. Presented here is a study for the development
of a new process to produce novel copolymer structures that
utilizes the topology of a polymer colloid specifically for
the purpose of chemically grafting hydrophilic polymer onto
hydrophobic polymer backbones. It is believed that this
copolymer is present as a hydrophilic polymer chain extend-
ing into the aqueous phase from the surface of a hydrophobic
polymer colloid onto which it is grafted.
One of the primary targets for this chemical modification
is the biomacromolecule cis-polyisoprene from natural rubber
latex (NRL). This polymer in its native form has many
special properties (such as being essentially 100% cis-
polyisoprene, which gives a mechanical response that makes
it well suited in applications such as surgical gloves).
However, it also has limitations, such as a colloidal stability
which is very sensitive to pH changes, and the presence of
proteins which can cause allergenic reactions.1 There are
clearly potential advantages in being able to carry out grafting
reactions using NRL in a seeded emulsion polymerization
* To whom correspondence may be addressed. E-mail: gilbert@
chem.usyd.edu.au.
† Present address: Department of Polymer Chemistry & Technology,
a number of such modifications reported in the literature (e.g.,
refs 2-15).
The “topology-controlled” process reported here combines
the particular topology in an emulsion polymerization with
the design made possible by free-radical chemistry, in a way
that should be applicable to any latex with appropriate graft
sites on the seed polymer. The grafting requires an extractable
hydrogen, such as present on the backbone of polyisoprene,
polybutadiene, and polystyrene. The objective is to create a
graft site at the particle-water interface, so that efficient
subsequent propagation from this graft site with a hydrophilic
monomer is then possible. In addition, a transfer reaction
leading to homopolymer in the water phase, and cross-linking
of the seed polymer, may also occur. This is shown
schematically in Figure 1.
To control the locus of radical formation, a redox initiation
system was selected consisting of a hydrophilic reducing
agent and a hydrophobic oxidizing agent. It was proposed
that a couple such as cumene hydrogen peroxide (CHP) and
tetraethylenepentamine (TEPA), hydrophobic and hydrophilic
species, respectively, will generate radicals mainly at the
polymer/water interface due to the partitioning of CHP and
TEPA primarily into the organic phase and aqueous phases,
respectively (as first adumbrated by Cockbain et al. in the
context of graft copolymers between NRL and methyl
methacrylate10,11). The grafting process can occur either
through abstraction or addition, as shown in Figure 2. Bulky

Eindhoven University of Technology, P.O. Box 513, 5600 MP Eindhoven, initiator radicals, such as the cumyloxy radical from the
The Netherlands. present system, favor abstraction compared to addition.16,17
10.1021/bm005654e CCC: $20.00 © 2001 American Chemical Society
Published on Web 04/27/2001
Modification of Natural and Artificial Polymer Colloids
Figure 1. Schematic of topology-controlled emulsion polymerization leading to graft copolymer. Water-phase polymerization to form homopolymer
of the water-soluble monomer, W, and cross-linking of the graftable seed polymer within the particle phase are also possible.
Figure 2. Abstraction and addition reactions which can lead to
grafting in systems with a labile hydrogen such as polyisoprene
(shown here), polybutadiene, and polystyrene. I ) initiating radical
(e.g., cumyloxy radical).
The primary cumyloxy radical will readily abstract protons
from the polymer backbone, creating a grafting site accessible
to aqueous monomer. Further addition of hydrophilic mono-
mer will extend the grafted chain into the aqueous phase. A
second criterion for effective grafting is that the monomer
to be used for the second-stage graft be sufficiently reactive
to propagate readily with the radical resulting from the
abstraction step. In the present case, that radical is allylic
(Figure 2), and hence it is essential to choose the second-
stage monomer to be sufficiently reactive: the stability of
the allylic radical may mean that it could have a very slow
Biomacromolecules, Vol. 2, No. 2, 2001 519
Figure 3. Structure of DMAEMA.
reinitiation rate coefficient with some monomers. Thus
monomers such as vinyl esters, where the radical is reactive
but the monomer is not, would be inappropriate, while
acrylates and, to a lesser extent, methacrylates are more
reactive monomers. The monomer chosen for this study was
dimethylaminoethyl methacrylate (DMAEMA, Figure 3),
although the process should work with any hydrophilic
monomer which is sufficiently reactive with the backbone
radical resulting from the grafting reaction. The resulting
graft block copolymer could be a simple branch or a comb.
In addition to any polyDMAEMA-graft-polyalkenylene
chains that may have formed, the initiation process is likely
to lead to cross-linking in a polyalkylene seed polymer, and
hence an increase in gel fraction is to be expected from the
procedure, whether or not the anticipated grafting occurs.
Three polymer systems have been chosen for study.
Polyisoprene was chosen due to the established ability of
520 Biomacromolecules, Vol. 2, No. 2, 2001
tert-butoxy and benzoyloxy radicals to abstract protons17,18
from its backbone in preference to the addition of such
radicals across residual double bonds. As the source of
polyisoprene in this work was natural rubber latex rather than
a synthetic polyisoprene latex, polybutadiene was selected
as a second target to provide a system that avoids the
complexities inherent with this natural polymer (high poly-
dispersity, protein groups, phospholipid content, etc.19-21)
while displaying analogous chemistry. Polystyrene was also
used as it affords the study of a system with slower diffusion
rates, particularly with respect to primary radical diffusion. 22
It is noted that the topology-controlled technique discussed
here can produce grafts of the hydrophilic monomer at any
point along the backbone of the hydrophobic substrate
polymer and, hence, is likely to result in a comb copolymer
(although the number of side units may well be small,
depending on the radical flux and grafting chemistry). It is
thus qualitatively different from the well-known emulsion
polymerization technique used to produce an electrosteric
stabilizer,23,24 which is a (largely) block copolymer formed
when hydrophobic and hydrophilic monomers are copoly-
merized in an emulsion polymerization (rather than the
grafting of hydrophilic monomer onto hydrophobic polymer
of the present technique). The electrosteric stabilizer is
formed by the hydrophilic monomer undergoing homo-
polymerization in the water phase, until it copolymerizes with
sufficient units of the (sparingly soluble) hydrophobic
monomer in the water phase that the radical end becomes
hydrophobic, enters the lipophilic region of a latex particle,
and continues polymerization with the large amount of
hydrophobic monomer in the particle interior.
Having noted the qualitative difference in synthetic
procedures and final molecular architecture, it should also
be noted that the present topology-controlled technique will
result in a copolymer which can also function as an
electrosteric stabilizer. Enhanced latex stability at low pH
(conditions under which the unmodified polybutadiene and
natural rubber latexes used in this study coagulate) was used
as one of the means to test for successful grafting. To verify
that changes in latex properties observed after the grafting
reaction were due to the presence of chemically grafted poly-
(DMAEMA), rather that the adsorption of poly(DMAEMA)
onto the latex particles surfaces (steric stabilization) or free
poly(DMAEMA) in solution (depletion stabilization),24 a
series of natural rubber latex samples with varying weight
fractions of added poly(DMAEMA), i.e., ungrafted homo-
polymer, was prepared and acidified, so that the colloidal
stability of these mixtures could be compared to those of an
analogous supposedly grafted system.
II. Experimental Section
A. Materials. Butadiene, sodium persulfate, sodium do-
decyl sulfate, sodium hydrogencarbonate, and dodecyl mer-
captan used in the preparation of polybutadiene were used
without further purification as supplied as reagent grade by
Aldrich. cis-Polyisoprene was obtained as ammoniated
natural rubber latex (“high-ammonia latex”, 60% solids) and
used as supplied by RLA Polymers. DMAEMA, CHP, and
Lamb et al.
Table 1. Preparation of Polybutadiene
compound amount (g) compound amount (g)
butadiene 45.08 NaHCO3 1.705
Na2S2O8 0.563 dodecyl mercaptan 0.558
SDS 6.022 water 175.01
Table 2. Preparation of Polystyrene Latex
compound amount (g) compound amount (g)
AMA-80 2.36 KPS 0.26
NaHCO3 0.25 H 2O 126.00
styrene 18.32
TEPA were also used as received without further purification
as reagent grade chemicals from Aldrich.
B. Preparation of Synthetic Latexes. Because of the
difficulties of analyzing for grafts onto natural rubber latex
(given the high polydispersity and large number of species
present), the topology-controlled methodology was also
applied to two synthetic latexes, where analysis of grafting
is easier.
1. Polybutadiene Latex. Polybutadiene seed latex was
prepared by free radical emulsion polymerization in a
modification of the method of Weerts et al.25,26 Sodium
persulfate (Na2S2O8) and sodium dodecyl sulfate (SDS) were
used as initiator and surfactant, with NaHCO3 as buffer. The
use of a chain transfer agent has been found to be essential
in the emulsion polymerizations of dienes both for initiation
and for control of the degree of branching and cross-
linking;25,26 dodecyl mercaptan was used for this purpose.
Materials were combined as indicated in Table 1, with the
addition of butadiene after the rest of the system was cooled
to approximately -60 °C in an acetone/dry ice bath. The
reaction vessel was then sealed and polymerization performed
in a bottle polymerizer with a rotation speed of 50 rpm and
a reaction temperature of 60 °C. This reaction was allowed
to proceed for a period of 20 h.
The resulting latex was found to have a solid content of
20% and a gel fraction of 47.5%. The gel fraction was
measured by allowing the dried polymer to dissolve in an
excess of tetrahydrofuran for a period of 2 weeks, before
the residual solid and solvent were separated and the solid
weighed.
2. Polystyrene Latex. The polystyrene seed used in the
present study was prepared using styrene, surfactant (AMA-
80, sodium dihexyl sulfosuccinate), and buffer (NaHCO3)
in the amounts shown in Table 2 and was left for 45 min at
90 °C. The potassium persulfate initiator was added as a
water solution and the system allowed to react in a bottle
polymerizer at 90 °C for 12 h. Although not measured in
this study, this formulation has been shown to reproducibly
form particles of approximately 50 nm in diameter; the latex
was measured to have a solid content of 14%. (It is noted
that, although the polystyrene is glassy under the conditions
of the experiment, there is more than enough time for the
CHP to diffuse throughout the polystyrene particles in the
1-h settling time and ensuing 2-h feed time used here. This
can be verified using the relation between average distance,
time, and diffusion coefficient, 〈r2〉 ) 6Dt, with D ) 10-18
m2 s-1 (typical for a monomeric-sized molecule in a glassy
Modification of Natural and Artificial Polymer Colloids
Table 3. Modification of Natural Rubber, Poly(butadiene), and
Poly(styrene) Latexes
amount (g)
NRL poly(butadiene) poly(styrene)
unmodified latex 155.78 75.13 52.74
DMAEMA 15.7 9.585 5.06
CHP 0.60 0.259 0.1521
TEPA 0.80a 0.1627b 0.1688c
NH3 (2.5%) 200 6.91d 50.36
a Made up to a 10% solution with distilled H O. b Diluted to 2.01 g with
2
distilled H2O. c Diluted to 14.5258 g with distilled H2O. d Diluted to 77.86
g with distilled H2O.
polymer27). One thus finds for a radius of ∼25 nm that the
diffusion time is ∼100 s, much less than the time over which
the experiment is performed.
C. Grafting Procedures. 1. Grafting Procedure for
Natural Rubber Latex. Natural rubber latex, DMAEMA,
CHP, and 2.5% ammonia solution were combined in the
amounts indicated in Table 3. The reaction mixture was
agitated with a low shear impellor at approximately 100 rpm
under a nitrogen atmosphere over a period of 1 h to allow
the partitioning of CHP into the rubber particles, before
injection of the TEPA solution. The TEPA solution was then
added shotwise over 1 h, at 5 min intervals, to initiate
polymerization. As with the polybutadiene modification, the
system was cooled in an ice/water bath during this process
and held at low temperature for the first 8 h of reaction before
gradual warming to room temperature and allowed to
continue to react for another 16 h.
2. Grafting Procedure for Polybutadiene Latex. The
seed polybutadiene latex, monomer (DMAEMA), 25%
ammonia solution, and CHP were added in the amounts
indicated in Table 3 under a nitrogen atmosphere and agitated
in the same manner as for the NRL preparation for a period
of 1 h to allow the CHP to partition inside the latex particles.
During this period the reaction was cooled to ∼4 °C using
an ice/water bath. TEPA was injected continuously using a
syringe pump into the system over a period of 1 h. The
temperature was held constant during the first 8 h of reaction,
after which the system was allowed to warm gradually to
room temperature and the reaction allowed to proceed for a
further 16 h. In a separate experiment, the reaction was
carried out in the same manner as above except the entire
reaction was performed at room temperature.
3. Grafting Procedure for Polystyrene Latex. The seed
polystyrene latex, DMAEMA, and CHP were added in the
amounts indicated in Table 3, and the mixture was agitated
under a nitrogen atmosphere at room temperature for 1 h.
TEPA was fed in using a syringe pump over 2 h to initiate
grafting, and the system was allowed to react for 24 h, again
at room temperature.
D. Analysis Techniques. 1. Poly(DMAEMA) Adsorp-
tion: Colloidal Stability Test. One indication that grafting
had occurred as predicted would be to see if the latex has
increased colloidal stability at low pH, since grafted poly-
(DMAEMA) chains should act as electrosteric stabilizers.
Since it is likely that some ungrafted poly(DMAEMA) will
also form, it is necessary to ensure that any enhanced
colloidal stability is not simply due to ungrafted homopoly-
Biomacromolecules, Vol. 2, No. 2, 2001 521
Table 4. Preparation of Poly(DMAEMA)
compound amount (g) compound amount (g)
oxalic acid 28 DMAEMA 50
water 100 thioglycolic acid 0.38
V50 40a
a As a 1% w/w solution in H2O.
mer. Poly(DMAEMA) was prepared using DMAEMA
monomer, thioglycolic acid (a chain transfer agent), oxalic
acid (for pH control), and V50 (2,2′-azobis(2-amidino-
propane) dihydrochloride) as initiator in the amounts indi-
cated in Table 4. The reaction was carried out over 2 h at
55 °C.
Addition of this poly(DMAEMA) to natural rubber latex
as a representative sample was carried out with the concen-
trations of poly(DMAEMA) varied between 0 and 5 wt %.
Each NRL sample contained 15 g of latex with 30% solids
content. The acidification was carried out by dropwise
addition of 1% HCl solution to the samples with agitation;
the pH was monitored throughout. The amount of coagulation
can be measured quantitatively in a number of ways, such
as turbidimetry. However, for the present purpose simple
visual inspection to see if coagulation had occurred was
deemed sufficient, since it was found that dramatic coagula-
tion occurred over a small range of pH.
2. Extraction and Analysis of Grafted Materials.
Separation of reaction products for analysis was performed
using Soxhlet extraction. The protocol for this procedure was
similar for each system. The latex was acidified by dropwise
addition of 6% HCl solution and dried thoroughly (in air at
60 °C over 24 h), and a two-stage extraction process was
carried out: first an extraction with acidified water and
second, after drying the latex, an extraction with toluene.
The use of acidic conditions in the extraction has been
shown28 not to cause hydrolysis of poly(DMAEMA) under
the conditions used here. The time for the extraction was
varied from 24 h for modified polybutadiene and NRL to
72 h for polystyrene. Gravimetry was carried out with the
modified NRL to see if an increase in water-soluble materials
was observed, as expected if significant amounts of ungrafted
poly(DMAEMA) were to be formed. There are thus three
separate phases for analysis: the water-soluble extraction,
which will contain any ungrafted poly(DMAEMA) and any
graft material which largely comprises poly(DMAEMA); the
toluene-soluble extraction, which will contain any ungrafted
polybutadiene and any graft material which largely comprises
polybutadiene; the insoluble gel, which by the double ex-
traction process can contain no ungrafted poly(DMAEMA).
Even though this homopolymer will be partitioned between
the water and organic phases, the double extraction process
will remove any poly(DMAEMA) that is not grafted.
1H and 13C solution NMR studies were performed using a
200 MHz Bruker spectrometer on the extraction products of
the modified polybutadiene and polyisoprene latexes using
D2O and CDCl3 as solvents. Solid-state NMR studies were
performed (by Dr. Andrew Whittaker at the Centre for
Magnetic Resonance, University of Queensland) using a
MSL300 spectrometer. For modified polybutadiene and
modified polyisoprene, this was on the fraction of polymer
remaining after the extractions had been completed.
522 Biomacromolecules, Vol. 2, No. 2, 2001
For the modified polystyrene, the reaction product was
first acidified and dried and then subjected to Soxhlet
extraction with acidified water for 3 days. The organic
Soxhlet extraction product was found to be largely insoluble
in CDCl3, in C6D6, and even in styrene monomer. Solid-
state NMR was performed on this organic fraction (after the
aqueous extraction).
III. Results and Discussion
A. Latex Properties. The modified polybutadiene and
polyisoprene latexes displayed dramatically enhanced col-
loidal stability on acidification as compared to the unmodified
latexes: the modified latexes were colloidally stable at pH
2. This is in contrast to the instability exhibited by the
unmodified samples, whereby the addition of just a few drops
of 6% HCl solution resulted in coagulation (i.e., unmodified
NRL is colloidally unstable when acidified to below pH 10).
It should, however, be noted that the modified polybutadiene
latex exhibited some flocculation several days after the
acidification had been performed. This might possibly be
attributed to bridging flocculation29 caused by high molecular
weight aqueous poly(DMAEMA) or simply to a decrease in
the stability ratio caused by the modification process.
It would be interesting to quantify the change in colloidal
stability by measuring the stability ratios of the NRL.
However, work in this group (by Mr. Fugang Li) has shown
that measuring these by the usual technique of plotting the
slope of the turbidity vs time curves30,31 at different elec-
trolyte concentrations cannot be used for NRL: reproducible
data cannot be obtained, presumably because of the extremely
broad polydispersity of NRL. Moreover, it is extremely
difficult to separate high molecular weight aqueous poly-
(DMAEMA) from (modified) small rubbery particles to test
the bridging-flocculation hypothesis. This is because separa-
tion by dialysis or by ultrafiltration will not completely
separate small particles from high molecular weight water-
soluble polymer, while centrifugation and subsequent redis-
persion of the washed centrifugate is impossible because
rubbery particles flocculate (irreversibly) when compacted
in the centrifugal field.
Varying the way in which the TEPA solution was injected
into the reaction (in shots or as a continuous feed) vessel
did not appear to have an effect on the stability of the end
latex to acidification, although increasing the period of time
over which the TEPA was injected did appear to result in a
larger degree of polymerization of the DMAEMA, based
qualitatively on the end viscosity. This would be expected
if the TEPA generates radicals that, while unable to
polymerize monomer, could be involved in termination
reactions. Increasing the time over which TEPA is injected
is equivalent to lowering the concentration of this terminating
radical species which would enable the poly(DMAEMA)
chains to increase in their degree of polymerization before
a termination event. It should be noted that the viscosity of
a polymer solution is increased not only by an increase in
the amount of polymer but also by its molecular weight.
Similarly to changing the injection technique, varying the
experimental temperature from the initial ice/water bath
Lamb et al.
Figure 4. 13C NMR spectrum of the modified polybutadiene organic
extraction product. Poly(DMAEMA) peaks indicated by the arrow.
temperature to room temperature yielded no observable
difference in the stability of the modified latex but did result
in a higher viscosity at the end of the 24 h reaction period.
This indicates that the formation of poly(DMAEMA) was
able to proceed to larger conversions at the higher temper-
ature simply by an acceleration of the reaction processes.
With the modified NRL, gravimetry results from the
aqueous extraction showed a 4% increase in the amount of
water-soluble material. This however is an inconclusive result
in terms of solubilizing polyisoprene into the water phase
by a grafting reaction, as (a) the nature of such gravimetric
measurements is subject to large uncertainties and (b) there
is an abundance of extraneous species in the natural rubber
latex which may have also been extracted.
B. Grafting or Adsorbed Polymer? The unmodified NRL
and polybutadiene latex samples before acidification had a
pH of 10, and for all cases (0, 1, 2.5, and 5% weight fraction
added poly(DMAEMA)), only a few drops of dilute HCl
solution (1%) to each small (15 mL) sample was required
before coagulum was observed and any noticeable change
in pH had occurred. Above 5%, the samples became too
viscous to perform the acidification. This indicates that the
increase in stability following the latex modification is not
due to poly(DMAEMA) adsorbing onto particles or acting
as a depletion stabilizer and, thus, provides evidence for the
presence of a grafted polymeric stabilizer.
C. NMR Studies. 1. 1H and 13C NMR Spectroscopy of
Soluble Fractions. 1H and 13C NMR spectra were obtained
for the aqueous and organic fractions of the extraction
process with the modified polybutadiene and polyisoprene
latexes. The aqueous fractions in both cases failed to show
any peaks other than those characteristic of poly(DMAEMA).
In the case of modified NRL, useful spectra of the organic
fraction could not be obtained due to difficulties in achieving
sufficient dissolution of polymer samples after the latex had
been dried. Figure 4 shows the spectrum obtained for the
organic fraction of the organic extraction from the modified
polybutadiene. In addition to the peaks expected from cis-
and trans-polybutadiene, this exhibits peaks at 63 and 65
Modification of Natural and Artificial Polymer Colloids Biomacromolecules, Vol. 2, No. 2, 2001 523

Figure 5. Solid-state 13C NMR spectrum of insoluble polybutadiene

extraction product from single pulse excitation. Arrows indicate
poly(DMAEMA) aliphatic carbon peaks.

Figure 6. Cross-polarization 13C NMR spectrum of modified poly-

ppm that are assigned to carbon environments adjacent to butadiene: (a) carbonyl carbon; (b) quaternary carbon for poly-
nitrogen groups, as expected with grafted poly(DMAEMA). (DMAEMA).
However, the intensities are extremely low and other
possibilities such as TEPA-derived radicals terminating on
the particle surfaces cannot be ruled out.
Spectra were unable to be obtained for the organic
extractions from the modified polystyrene latex due to the
dried latex exhibiting extremely low solubility in a wide
range of solvents.
2. Solid-State NMR Spectroscopy. 13C solid-state NMR
was performed for all three modified polymer systems.
Single-pulse 13C spectra were measured with a magic-angle
spinning speed of 2.5 or 4 kHz with a recycle-delay time of
4 s; cross-polarization 13C spectra were also measured, with
a contact time of 2 ms. It is repeated that any peaks
corresponding to poly(DMAEMA) in the gel fraction can
only arise from grafting having occurred with the seed
polymer.
Evidence of poly(DMAEMA) was found in all three Figure 7. Cross-polarization 13C NMR spectrum of insoluble portion
polymer samples. Figure 5 shows the single pulse excitation remaining after double extraction from modified NRL. Arrow indicates
13C spectrum of modified polybutadiene and gives evidence poly(DMAEMA) quaternary carbon peak.
for the presence of both polybutadiene and poly(DMAEMA).
The large peaks in the spectrum are characteristic of
considerably less poly(DMAEMA) was present in this case
polybutadiene but the smaller peaks between 50 and 65 ppm
than in the modified polybutadiene sample.
and those between 20 and 30 ppm are characteristic of the
aliphatic carbons of a methacrylate-type polymer. Upon the On the basis of the size of the quaternary carbon peak,
basis of the number of aliphatic carbons that each type of observed to be an order of magnitude smaller than that in
repeating unit possesses, this area was integrated to give the the modified polybutadiene, the amount of grafted poly-
relative proportion of grafted poly(DMAEMA) to poly- (DMAEMA) in NRL is estimated at 1-2%.
butadiene. This integration indicated that the grafted ma- The amount of grafted material in the modified natural
terial comprised approximately 12% of the total material rubber sample as measured by solid-state NMR spectroscopy
present. is a factor of ∼10 less than that for polybutadiene. This result
The cross-polarization experiment of the gel fraction left may be rationalized by noting that the amount of grafting
after double extraction of the modified polybutadiene, Figure onto the latex should be a function of the latexes particle
6, shows the poly(DMAEMA) carbonyl peak at 178 ppm size distributions and proportional to (area/mass) ∼ (radius)-1.
and the quaternary carbon at 45 ppm, further verifying the The average particle radius in a typical natural rubber latex
presence of grafted polymer. is ∼1 µm,21,32 while that of the polybutadiene latex prepared
The single-pulse 13C spectrum of the modified natural with this technique is ∼50 nm. Although NRL is highly
rubber latex sample showed little conclusive evidence of polydisperse and contains many small particles, it is the more
poly(DMAEMA) presence in the sample. However, the massive particles that will largely determine the observed
cross-polarization spectrum (Figure 7) shows the quaternary amount of grafting. Indeed, evaluating the average of r-1
carbon as a small peak at 45 ppm and does provide firm for the NRL particle size distribution determined experi-
evidence for successful grafting. It was also apparent that mentally by Li et al.32 gives (250 nm)-1, compared with (50
524 Biomacromolecules, Vol. 2, No. 2, 2001
Figure 8. Cross-polarization solid state 13C NMR spectra of modified
polystyrene. Arrows indicate polystyrene aliphatic peaks.
nm)-1 for the polybutadiene latex. This difference of a factor
of 5 is consistent with the observed amounts of grafted
polymer.
Figure 8 shows the 13NMR cross-polarization spectrum
of the product from modified polystyrene following aqueous
extraction. This spectrum indicates that grafting had been
achieved for polystyrene with the poly(DMAEMA) peaks
evident at 0-30 and 49-80 ppm. The aliphatic region of
the spectra was integrated in the same manner as modified
polybutadiene and polyisoprene samples to yield a content
of poly(DMAEMA) present in the sample of 35%.
The larger amounts of apparent graft polymer in this
styrene system compared to the modified polybutadiene and
polyisoprene systems can be attributed in part to slower
diffusion of primary cumyloxy radicals away from the
particle surface to result in an increase in the amount of graft
sites accessible to the DMAEMA monomer. Another expla-
nation is a higher rate coefficient for the abstraction and/or
subsequent propagation steps.
D. Mechanistic Interpretation. The proposed mechanism
for the grafting process in given in Figure 1. Control of the
loci of radical formation and of subsequent polymerization
is considered to be the crucial step in this procedure. To
graft a hydrophobic monomer successfully onto a hydrophilic
polymer colloid, a grafting site must be created in an area
that is accessible to monomer. We postulate that this is
achieved by using a redox couple with a highly hydrophilic
component and a highly hydrophobic component. Under
these circumstances, the majority of primary radicals should
be formed at the surface of the particles where the two phases
meet and the peroxy radical can create a graft site by
hydrogen abstraction from a polymer backbone. Monomer
can be grafted by subsequent propagation from this site. The
data are certainly consistent with this postulate as a major
mechanism.
The fact that the polystyrene exhibits more grafting than
polybutadiene or polyisoprene suggests (although does not
prove) that diffusion of primary cumyloxy radicals away
from the particle surface into areas low in concentration in
hydrophilic monomer is also an important factor. Polystyrene
is glassy at the experimental conditions (swelling by
DMAEMA and CHP is unlikely to lower its Tg from 100
°C to the reaction temperature range of 4-25 °C); hence
Lamb et al.
diffusion of radical species in the polymer matrix should be
significantly slower than that for the other rubbery systems.
The grafting efficiency is of course dependent on rate
coefficients as well as on topology.
The primary radical species derived from TEPA on
reaction with an acyl peroxide is not known, and its effect
on the overall reaction scheme is thus hard to quantify. It is
postulated here that there is the formation of a nitrogen-
centered radical, a species known to have slow rates of
addition to alkenes.33 This radical is therefore expected to
be water-soluble and to act primarily as a terminating species,
as has been proposed previously34,35 along with the redox
reaction of TEPA with solvated metal ions.36 However it
has also been postulated37,38 that a carbon-centered radical
may be formed in the R position for similar redox systems
such as dimethylaniline with benzoyl peroxide, which may
lead to polymerization. Moreover, the role of metal ions in
the aqueous phase and their effect on the reaction kinetics
have not been elucidated, and it is possible that the species
arising from hydrophobic/hydrophilic redox-couple initiation
which causes the abstraction may be different from that
suggested by the foregoing considerations.
IV. Conclusions
A technique has been devised which should result in the
formation of graft, block, or comb copolymers between a
hydrophobic polymeric seed and a hydrophilic second-stage
polymer, using the topology of a seeded emulsion poly-
merization. The latex formed when natural rubber and
polybutadiene latexes are modified by seeded emulsion
polymerization with a hydrophilic monomer (DMAEMA)
is very colloidally stable in acidic conditions; this is good
evidence that a steric or electrosteric stabilizer has been
attached to the surface of the particles and hence that a graft
polymer has been formed. The solid-state 13C NMR spectra
of insoluble products left after extraction with water and
toluene in sequence, and the inability of free aqueous
poly(DMAEMA) to enhance latex stability, show that a
significant amount of this is a grafted hydrophilic polymer
layer, not adsorbed poly(DMAEMA), and further it is likely
that a significant fraction of this grafting occurs at the
particle/water interface. It also appears that the diffusion of
the initiating species from the particle surface is an important
factor in this process.
These results support the proposed mechanism for block
copolymer formation by radical production at particle
surfaces and subsequent polymerization of aqueous monomer
into the water phase. This opens the way to novel modifica-
tions of polymer colloids, in particular those from natural
rubber latex, to make new materials previously unobtainable
with current techniques. Optimization of mechanical proper-
ties will require control of processes such as the number and
size of grafts, and of side reactions such as extraparticle
homopolymerization and intraparticle cross-linking, both of
which can also arise from the reactions shown schematically
in Figure 1.
Acknowledgment. Dr. H. De Bruyn is thanked for
synthesizing the polystyrene latexes. We greatly appreciate
Modification of Natural and Artificial Polymer Colloids
the collaboration of Dr. Andrew Whittaker for the collection
and interpretation of the solid-state NMR spectra. The Key
Centre for Polymer Colloids is established and supported
under the Australian Research Council’s Research Centres
Program.
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