Macroporous Monolithic Poly(4-vinylbenzyl chloride)

Columns for Organic Synthesis Facilitation by In Situ

Polymerization of High Internal Phase Emulsions
SEBASTIJAN KOVAČIČ, PETER KRAJNC

Laboratory for Organic and Polymer Chemistry, Faculty of Chemistry and Chemical Engineering, University of Maribor,
Smetanova 17, SI 2000 Maribor, Slovenia

Received 4 August 2009; accepted 10 September 2009

DOI: 10.1002/pola.23732
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: PolyHIPE materials are produced by polymerizing the continuous phase

of emulsions where the internal phase volume fraction is higher than 74%. Columns
of flow-through supports for immobilized scavengers and reagents were prepared by
polymerizing the continuous phase of high internal phase emulsions containing
4-vinylbenzyl chloride and divinylbenzene. Emulsions were placed in containers and
polymerized in situ. Highly porous (80% pore volume) monolithic columns with chlor-
omethyl functionalities and crosslinked with divinylbenzene (6% or 40%) were
obtained and functionalized by a flow-through method, immobilizing tris(2-amino-
ethyl)amine, diethanolamine, and 4-bromophenylboronic acid. Columns with immobi-
lized tris(2-aminoethyl)amine were applied for the effective removal of acid chlorides
from the solution pumped through the column. Flow properties (back pressure versus
flow rate) were characterized for dichloromethane, N,N-dimethylformamide and ace-
tonitrile. High effectiveness of columns were demonstrated by an over 90% of acid
chloride removal from the solution after a single pass-flow of the solution through
the column. The morphology of the column material was characterized by scanning
electron microscopy and showed no damage of the material after the flow-through
utilization. Good permeative properties of the interconnected porous structure make
polyHIPE columns good candidates for supports for reagents and catalysts. V C 2009

Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6726–6734, 2009
Keywords: high internal phase emulsion; macroporous polymers; polymer
monoliths; polyHIPE; solid phase filtration

INTRODUCTION tide synthesis using a polystyrene based support.1

The concept of using crosslinked insoluble poly-
mers as supports for the attachment of reagents,
catalysts and scavengers and thus facilitate
organic synthesis, is well known and has gone a
long way since Merrifield’s publication of a dipep-
Correspondence to: P. Krajnc (E-mail: peter.krajnc@
uni-mb.si)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, 6726–6734 (2009)
V
C 2009 Wiley Periodicals, Inc.
6726
Solid phase organic synthesis (SPOS) has been
revitalized by combinatorial chemistry principles
in the 1990s.2,3 The large number of variety of
uses of polymer supports, being anchors for
reagents, catalysts, or scavengers (species for the
removal of excess reagents), can be found in the
literature.4 Even multi-step syntheses of natural
products can be conducted using polymer sup-
ports in several steps.5 The use of reagents or cat-
alysts, tethered to insoluble polymers, brings
some noticeable advantages over their low
 POLYMERIZATION OF HIGH INTERNAL PHASE EMULSIONS
molecular weight analogues. The isolation is done
simply by filtration and normally there is no need
for further purification apart from washing the
polymer support. With well defined reactions
automation is possible, which is demonstrated by
numerous examples of parallel synthesis. Large
excesses of reactants can be used when this is
beneficial for the completion of the reaction.
Crosslinked polymers, typically beads of diame-
ters between 20 and 200 lm prepared by suspen-
sion polymerization, are introduced in the solvent
and the reaction is carried out in the same man-
ner as traditionally with the lower molecular
weight compounds. Reactions using polymer sup-
ported species can be carried out in a flow through
manner rather than in a batch type setup. The
flow principle usually offers even easier handling
with the polymer supports, being positioned in a
container. There is less probability for the damage
of the polymer support and more possibilities for
process automation and even the use of more sup-
ports in a row is envisaged. With a flow-through
setup, there are fewer problems with polymer-sol-
vent compatibility. High throughput, minimum
workup and continuous operation are another
welcome features.
Over thirty years ago first attempts (apart
from using ion exchange resins) of applying this
principle to organic synthesis were made, how-
ever not many examples followed at that time.6
Recently, the number of reports on using flow-
through type polymer supports setups is grow-
ing.7 The groups of Prof. Ley from Cambridge and
Prof. Luis from Castello de la Plana in particular,
have recently published a number of reports on
the utilization of polymer supports in a flow mode
for organic synthesis.8 Especially promising
seems the preparation of monolithic polymer sup-
ports as they have good characteristics for the
flow-through setups. Monolithic supports, consist-
ing of a one piece of polymer mean much easier
handling procedures when used in a column com-
pared to particulate supports. Passing of flow in
between particles reduces the efficiency of the
support.9 The most noticeable difference between
monolithic and particulate supports in flow
through applications is the principle of mass
transfer. While diffusion limits the kinetics in
case of particles, in the case of porous monoliths
convection is the main principle of mass transfer.
Monolithic polymers are therefore already estab-
lished as chromatography columns,10 while vari-
ous types of monoliths for different applications
via flow through set-ups have also been
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
6727
described.11 Micro fluidic devices also utilize mon-
olithic polymers.12,13
For efficient flow through columns, larger pores
are beneficial however for a greater capacity
higher surface is required and thus smaller pores.
One way to overcome this is by grafting reactive
groups onto a support with large pores.14,15
Another important issue is ensuring tight fit of
the polymeric monolith inside a column to prevent
the flow passing at the sides of the column.
Kirschning et al. have prepared a glass polymer
composite where precipitation of polymer inside
the voids of porous glass is used.16 Bulk polymer-
ization with the aid of porogenic solvents is usu-
ally used for the preparation of porous polymeric
monoliths. Pore size distribution can be well con-
trolled however in the case of larger pieces heat
transfer during the polymerization can pose a
problem.17 Another way to produce highly porous
monolithic polymers is to utilize a high internal
phase emulsion. In such an emulsion, the dis-
persed phase takes up a high fraction of volume,
typically over 74%, which is the volume of the uni-
form beads packed in the densest way. In the case
of an even higher volume fraction of the dispersed
phase, the droplets become geometrically dis-
torted and the size distribution of diameters
becomes wider. If monomers are included in the
continuous phase of a high internal phase emul-
sion, by triggering the polymerization while pre-
venting the emulsion to phase separate, a highly
porous permeable polymer material can be
obtained (called polyHIPE material).18 The poros-
ity and morphology of the resulting polymer can
be tuned by the variation of several factors.19 The
typical structure of the material results from the
droplets of the internal phase being caught in
between the polymerizing continuous phase creat-
ing large spherical pores with the diameters close
to the diameters of the droplets of the emulsion
prior to polymerization (the droplets can grow
considerably bigger during the polymerization
due to emulsion instability). Moreover, the
smaller interconnecting pores are formed yielding
a highly interconnected, permeable structure.
These are probably formed during the polymeriza-
tion of the continuous phase due to the difference
in the densities of the solution of monomers and
polymer resulting in shrinkage and thus rupture
of the polymer film.20 Some reports suggest
that the interconnecting pores are the result of
the polymer post polymerization treatment.21
Usually, monolithic polymeric materials are pre-
pared from HIPEs. Recently, new developments
6728 KOVAČIČ AND KRAJNC
demonstrated the preparation of polyHIPE beads
(prepared by the suspension of HIPEs into a third
phase)22–24 and even membranes.25,26 PolyHIPEs
have been prepared from either oil in water27–29
or water in oil emulsions19 and have been used in
a flow through manner as scavengers,30
reagents31 and chromatography supports.32
In this article, we report a technique for pre-
paring columns by polymerizing HIPEs in situ
and utilizing novel columns for the removal of
acid chloride and immobilizing boronic acids via
flow-through methods.
EXPERIMENTAL
Materials
4-Vinylbenzyl chloride (VBC, Aldrich), divinyl-
benzene (DVB, Aldrich, 80%, tech.), and sty-
rene (Merck) were passed through the Al2O3
column before use to remove the inhibitors. Po-
tassium persulphate (KPS), sorbitan monooleate
(Span 80), tris(2-aminoethyl)amine, diethanol-
amine (DEA), benzoyl chloride (99%), 4-bromo-
phenylboronic acid were all purchased from
Aldrich and used as received. N, N-dimethylfor-
mamide (DMF), calcium chloride hexahydrate
(CaCl2
6H2O) and triethylamine were purchased
from Merck and used as received. Dichlorome-
thane (DCM, Aldrich) was distilled and stored
over molecular sieves. Housing used as the
polymerization mold was made from polyaryle-
theretherketone (PEEK) with the outer diame-
ter of 15 mm, length of 45 mm and volume
8 mL (CIMV IDA-8 mL Tube Monolithic Col-
R
umn, BIA Separations, Ljubljana, Slovenia).
The design of the housing forces the liquid to
flow in a radial direction. The mobile phase
entering the tube monolithic column is directed
into a helical groove drilled inside the housing
body, which distributes mobile phase over the
entire monolith.
Preparation of VBC/DVB/Styrene polyHIPE
Columns from Water-In-Oil High Internal
Phase Emulsions by In Situ Polymerization
3.48 g (22.80 mmol) of 4-vinylbenzyl chloride,
2.45 g (23.52 mmol) of styrene, 0.41 g (3.15
mmol) of divinylbenzene (or 4 g (30.7 mmol) in
the case of 40% crosslinked polymer), 1.11g of
sorbitan monooleate were placed in a reactor
and the mixture was stirred with an overhead
stirrer at 400 rpm. The emulsion was obtained
Journal of Polymer Science: Part A: Polymer Chemistry
by adding drop wise an aqueous solution of cal-
cium chloride hexahydrate (1.75 wt %) and
potassium persulphate (0.19 wt %) to the organic
phase under stirring. Once all the aqueous phase
has been added stirring was continued for fur-
ther 1 h, until a uniform W/O high internal
phase emulsion (HIPE) was obtained. HIPE was
injected into the column with a syringe and
cured at 70  C for 48 h. Resulting polyHIPE col-
umns were purified by pumping 1000 mL of
ethanol and 1000 mL of de-ionized water
through the columns at a flow rate of 2 mL/min.
For the determination of swelling characteristics,
polyHIPE samples were grinded and suspended
in the solvent for 24 h. The swelling degree was
calculated as the ratio of swollen volume to the
volume of dry material.
Functionalization of Columns via
Flow-Through Method
Six grams (41.0 mmol) of tris(2-aminoethyl)amine
and 6.00 g (59.3 mmol) of triethylamine [or 8.00 g
(76.1 mmol) of diethanolamine and 8.00 g
(79.1 mmol) of triethylamine in the case of func-
tionalization with diethanolamine]) were dis-
solved in 375 mL of a mixture of N,N-dimethylfor-
mamide and de-ionized water (volume ratio 4:1).
Solution was passed through the columns for 24 h
at a flow-rate of 2 mL/min. Solutions and columns
were kept at 60  C. After the functionalization the
columns were washed by pumping through
100 mL of a mixture of N,N-dimethylformamide
and deionized water (volume ratio 4:1) and 100
mL of dichloromethane.
FTIR spectra of the polymers were recorded on
a Perkin–Elmer FTIR 1650 spectrometer (KBr
pellets) and CHN elemental analyses were done
on a Perkin–Elmer CHN 2400 analyzer.
Removal of Benzoyl Chloride from Solution
560 mg (4.0 mmol; at a molar ratio of NH/NH2
groups to acid chloride 1:1) or 110 mg (0.8 mmol;
at a molar ratio of NH/NH2 groups to acid chlo-
ride 5:1) of benzoyl chloride was dissolved in 50
mL of anhydrous dichloromethane and was
passed through the column (1.80 g; 4 mmol of
NH/NH2 groups) at a flow rate of 2 mL/min. Con-
centration of benzoyl chloride in the eluant was
measured by absorbance at 240 nm with Varian
Carry 1E UV-ViS spectrophotometer.
DOI 10.1002/pola
 POLYMERIZATION OF HIGH INTERNAL PHASE EMULSIONS
Immobilization of 4-Bromophenylboronic Acid
Six hundred milligrams (3.0 mmol) of 4-bromo-
phenylboronic acid was dissolved in 250 mL of an-
hydrous dichloromethane and passed through the
column (5 mmol of amine groups) at a flow rate of
1 mL/min. After the functionalization the columns
were washed by pumping through 200 mL of
dichloromethane.
The amount of bromine in the polymer sup-
ports was determined by combustion under oxy-
gen (Pt catalyst) followed by ionic chromatogra-
phy with a system consisting of Varian ProStar
pump, 20 lL injection loop (manual injection),
Dionex IonPac AS12A column (4 mm), Dionex
ASRS Ultra II (4 mm) supressor column, and Dio-
nex CD20 conductivity detector using a mobile
phase with 2.7 mM Na2CO3 and 0.3 mM NaHCO3
at a flow rate of 1.5 mL/min and 12.5 MPa.
RESULTS AND DISCUSSION
Preparation of Columns and Flow Profiles
4-Vinylbenzyl chloride- (VBC) based polymers are
the most versatile and most frequently used poly-
mers for solid phase organic synthesis (SPOS)
and polymer assisted solution phase (PASP) prin-
ciples. The chloromethyl groups enable easy post
polymerization functionalization of the polymer
and this makes VBC-based polymers attractive as
polymer supports for reagents and catalysts. The
post polymerization functionalization methods are
advantageous over preparing functional mono-
mers in a way that the polymerization is done in
an established manner resulting in desired poly-
mer morphology and there is no need for altering
the polymerization conditions due to different
monomers. This is especially important in the
case of polyHIPE preparation as any change in
the monomer structure can result in lowered
emulsion stability and subsequently phase sepa-
ration during the polymer preparation. VBC was
therefore the monomer of choice for our investiga-
tions. Furthermore, polyHIPEs based on 4-vinyl-
benzyl chloride have been prepared by our group
and others and the influences of the emulsion for-
mulation on morphology have been described.33
To prepare columns of VBC-based polyHIPEs,
containers commercialized for the chromato-
graphic purpose were chosen (by BIA Separations,
Ljubljana, Slovenia). The construction of the con-
tainer enables radial flow (through helical
channels at the walls of the container) rather
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
6729
than longitudinal where there is always a possi-
bility of a bypass flow of the solution at the sides
of the column due to the shrinkage and poor
adherence of polymer to the inner walls of the
container.
Furthermore, because of the highly porous and
permeable polyHIPE structure, a convective mass
transfer rather than diffusive is achieved. This is
very important considering the aims of high
throughput methods and possibilities of automa-
tion. To characterize the flow of solvent through
the polyHIPE columns, VBC-based HIPEs with
80% of aqueous phase were prepared, containing
different degrees of crosslinking monomer divinyl-
benzene, namely 6% mol and 40% mol. This was
to determine the influence of crosslinking degree
on the robustness, back pressure, and site accessi-
bility of the monoliths. The percentage of VBC in
the organic phase was 50% mol in the case of
lower crosslinking degree and 40% mol in the case
of a higher crosslinking degree (styrene being the
remaining monomer). Scanning electron micros-
copy was used to observe the material’s morphol-
ogy (Fig. 1), which was typical of polyHIPEs with
big pores averaging approximately 3 lm in diame-
ter and with interconnecting pores averaging
approximately 0,8 lm in diameter. To test the
material’s behavior (with regards to swelling) in
solvents, parts of the monolithic polyHIPE mate-
rials were powdered and suspended in dichloro-
methane, dimethylformamide, or acetonitrile and
the swollen volume was measured. The material
with a lower crosslinking degree (6%) has swollen
considerably in dimethylformamide and dichloro-
methane but less in acetonitrile (Table 1). The
polyHIPE with a higher degree of crosslinking
(40%) exhibited lower swelling, which was
expected due to a higher crosslinking degree.
Swelling behavior was reflected in the flow
characteristics of the columns. The column pre-
pared with a 6% crosslinked material had consid-
erably higher back pressures compared to the col-
umn prepared with a 40% crosslinked material.
When acetonitrile was pumped through the col-
umn with a lower crosslinking degree, the back
pressure remained low (under 0.2 MPa) until rea-
sonably high flow rates (4 mL/min; see Table 2).
In the case of dichloromethane the back pressure
reached maximum allowed (as stated by the con-
tainer producer- 5.5 MPa) pressure at a flow rate
of 3.5 mL/min, while in the case of DMF even at a
lower flow rate (2 mL/min). We believe this
reflects the swelling of the polymer and thus
blocking the interconnecting pores inside the bulk
6730 KOVAČIČ AND KRAJNC
Figure 1. SEM image of a VBC based polyHIPE
material polymerized inside the column (on enlarge-
ment, arrow points to an interconnecting pore while
the circle shows a bigger pore produced in the place
of a droplet of the internal phase of emulsion).
of the material. For the 40% crosslinked material,
the swelling degrees were lower, reflecting the
higher rigidity of the polymer chains. The 40%
crosslinked columns were therefore more appro-
priate for higher flow rates in various solvents, up
to 4 mL/min; at this flow rate the back pressure
was only 0.1 MPa for acetonitrile, 0.4 MPa for
dichloromethane and 0.7 MPa for dimethylforma-
mide. An HPLC system was used for performing
these measurements due to ease of flow rate set-
tings and back pressure measurements. However,
due to relatively low back pressures, the use of
Journal of Polymer Science: Part A: Polymer Chemistry
less sophisticated equipment for pumping is
envisaged, like peristaltic pumps or even gravity
driven flow. To make sure there was no damage to
the polyHIPE material inside the column after
the flow of solvent, samples were taken for SEM
analysis after the column was used by pumping
through solvent with different polarities. After
inspection no damage was found, either macro-
scopically and under SEM investigation. Only
when dimethylformamide was used and the flow
rate was set at 4 mL/min, the 6% crosslinked ma-
terial was damaged to the point of visible cracks.
The back pressures of columns with relation to
crosslinking degree and solvent are presented in
Table 2. Both 6% crosslinked and 40% crosslinked
materials were analyzed by FTIR spectroscopy
and the chlorine amount was determined. The
loading of chloromethyl groups for the 6% cross-
linked support was found to be 1.73 mmol per
gram and 1.06 mmol per gram for the 40% cross-
linked material. These are considerably lower
loadings then one would expect from the amount
of starting VBC in the polymerization emulsion
(50 mol % for the 6% crosslinked and 40 mol % for
the 40% crosslinked material). This is probably
due to the hydrolysis of the chloromethyl groups
during the polymerization. It has been reported
that during the polymerization, a significant
amount of chloromethyl groups undergo hydroly-
sis and this is especially intense for the 4-vinyl-
benzyl chloride monomer.34 Strong absorption
band at 3400 cm 1 in FTIR spectrum confirms
this conclusion. However, although this process
lowers the starting loading of the polymer, it may
have positive effects in terms of greater solvent
compatibility, making the polymer matrix par-
tially hydrophilic.
Functionalization of Columns and Scavenging
Experiments
Columns for flow through methods can be particu-
larly useful for immobilizing reagents for trans-
formations or for the removal of excess reagents
from the solution. To prepare a column for scav-
enging electrophilic compounds from the solution,
tris(2-aminoethyl)amine was applied as a func-
tionalizing agent, already known as a high
capacity scavenger.30,35 It is known to react read-
ily with the chloromethyl groups in the polymer
matrix. Furthermore, three amino groups of the
reagent increase the loading of the reactive
groups in the polymer after the functionalization
(Scheme 1).
DOI 10.1002/pola
 POLYMERIZATION OF HIGH INTERNAL PHASE EMULSIONS 6731

Table 1. Swelling Properties of Powdered polyHIPE
Materials (Ratios of Volume of Swollen Material/
Volume of Dry Material)
Cross-Linking
Degree (% mol) DMF DCM CH3CN
6 3.4 4.8 2.4
40 2.8 3.0 2.1
A flow through procedure was applied for the
functionalization process, pumping a solution of
tris(2-aminoethyl)amine in dichloromethane
through an in-mold polymerized polyHIPE col-
umn with a 6% crosslinked VBC based material
(1.73 mmol of chloromethyl groups per gram of
polymer). After a thorough wash, the polymer
from both ends of the column was taken for FTIR
and elemental analysis. Nitrogen contents for the
polymer from both ends of the column was very
similar and the difference can be seen within the
analysis error margins (5.14% of nitrogen was
found for the polymer at the flow-in end of the col-
umn and 5.39% was found for the polymer at the
flow-out end of the column). This suggests a
homogeneous conversion to tris(2-aminoethyl)-
amino derivative with the loading of 2.8 mmol of
primary or secondary amine groups per gram of
polymer. It is somewhat speculative to state the
conversion percentage to tris(2-aminoethyl)amine
derivative from the nitrogen amount present in
the polymer as additional crosslinking via the sec-
ond amino group in the tris(2-aminoethyl)amine
can occur thus lowering the amount of nitrogen
[one molecule of tris(2-aminoethyl)amine reacts
with two chloromethyl groups]. Amine functional-
ized column was used, in a flow-through manner,
to scavenge benzoyl chloride from the solution in
anhydrous dichloromethane. Firstly, an experi-
ment was performed to determine the capacity of
the column for benzoyl chloride under flow-
through conditions. For this purpose, a solution
with an excess of benzoyl chloride in relation to
the amine groups in the polymer was used. UV
spectroscopy was applied for the determination of
concentration of benzoyl chloride. No change in
the acid chloride concentration was noticed for
the solutions after the first and second run
through the column and therefore it was con-
cluded that the amount of benzoyl chloride scav-
enged corresponded to the actual capacity of the
column. This was found to be 1.2 mmol of acid
chloride per gram of polymer. From the deter-
mined nitrogen amount in the column (2.8 mmol
of primary or secondary amine groups per gram of
polymer), it can be concluded that the majority of
amine groups in the polymer are accessible to the
benzoyl chloride in the solution. It has to be noted
that the catch reaction of 1 mol of benzoyl chloride
releases 1 mol of HCl, which is also scavenged by

Table 2. Flow Properties of polyHIPE Columns

Back Back Back

Flow Rate Pressure Pressure Pressure Crosslinking
[mL min 1] [MPa] CH3CN [MPa] DCM [MPa] DMF Degree [mol %]

0.5 0.05 0.05 0.3 6

1 0.05 0.1 1
1.5 0.05 0.2 1.7
2 0.05 0.3 [5.5a
2.5 0.05 0.3
3 0.1 0.4
3.5 0.1 [5.5a
4 0.2
0.5 0.05 0.05 0.05 40
1 0.05 0.05 0.05
1.5 0.05 0.05 0.1
2 0.05 0.1 0.2
2.5 0.05 0.1 0.4
3 0.1 0.2 0.5
3.5 0.1 0.3 0.6
4 0.1 0.4 0.7
a
Max. allowed column pressure.

Journal of Polymer Science: Part A: Polymer Chemistry

DOI 10.1002/pola
6732 KOVAČIČ AND KRAJNC
Scheme 1. Functionalization of polyHIPE columns.
amine groups. This further suggests that the flow
of solution through the column actually proceeds
through the polymer monolith and not escaping
at the interface of monolith/mold bypassing the
actual polymeric monolith.
Similar experiment was performed to deter-
mine the dynamics of the removal of benzoyl chlo-
ride via the flow-through procedure. This time,
the excess of amine groups in the polymer
(approximately fivefold), was used. The solution of
benzoyl chloride was passed through the column
(2.8 mmol of amine groups per gram of polymer;
5.1 mmol of amine groups per column) repeatedly
four times. After the first run approximately 95%
of benzoyl chloride had been removed (Table 3),
while almost complete removal was achieved after
the fourth run. The reactions were monitored by
UV spectroscopy (determination of benzoyl chlo-
ride concentration) and FTIR spectroscopy (poly-
mer after scavenging reaction; formation of amide
bond absorptions). The results suggest efficiency
and ease of use of such a flow-through setup for
Journal of Polymer Science: Part A: Polymer Chemistry
the methods of polymer assisted solution phase
chemistry as the majority of the reagent had been
removed in the first run through the column.
Boronic acids are widely used in Suzuki type
coupling reactions where carbon–carbon bonds
are formed. Diethanolamine can be used to react
with boronic acids, therefore functioning as the
anchor to remove excess boronic acids from the
solution. Diethanolamine can be immobilized to a
4-vinylbenzyl chloride based polymer via the
nucleophilic attachment of the amino group.36,37
Therefore, such a derivative had to be prepared
prior to boronic acid immobilization. This was
achieved similarly to tris(2-aminoethyl)amine
derivative, by simply passing a solution of dietha-
nolamine through the column with VBC based
polyHIPE support (Scheme 1). In the case of the
lower crosslinking of the starting polymer, a de-
rivative with a loading of 2.5 mmol of diethanol-
amine groups per gram (calculated from nitrogen
content) was obtained suggesting an almost com-
plete conversion of chloromethyl groups, while
DOI 10.1002/pola
 POLYMERIZATION OF HIGH INTERNAL PHASE EMULSIONS
Table 3. Removal of Benzoyl Chloride from Solution
in Dichloromethane by Tris(2-aminoethyl)amine
polyHIPE Derivative
Percentage of Acid
Flow Cycle Chloride Removed
1 94.7
2 97.0
3 97.5
4 98.0
in the case of the support with a higher crosslink-
ing degree a diethanolamine derivative with
0.8 mmol of diethanolamine groups per gram was
obtained suggesting an incomplete conversion
(approximately 80% conversion calculated from
nitrogen content).
To immobilize the 4-bromophenylboronic acid
to the diethanolamine derivative the solution of
4-bromophenylboronic acid in anhydrous dichloro-
methane was passed through the column with
diethanolamine derivative (6% crosslinking
degree) at a flow rate of 1 mL/min. The amount of
4-bromophenylboronic acid attached was deter-
mined by elemental analysis of bromine content
in the polymer. Furthermore, FTIR spectroscopy
of the polymers was used to monitor the transfor-
mation. Bromine analysis suggested a high level
of immobilization yield for the support with a
lower level of crosslinking (8.8% of bromine was
found while 13.5% would indicate a complete con-
version); however, a slight excess of diethanol-
amine groups on the polymer support with
regards to the boronic acid in the solution was
used.
CONCLUSIONS
Monolithic porous permeable polymer supports
have a lot to offer to synthesis methods. Flow
methods with columns further simplify the proce-
dures and suggest the possibilities of automation.7
We have demonstrated that an ‘‘in-mold’’ polymer-
ization of high internal phase emulsions including
a reactive monomer can be a prospective tech-
nique for the preparation of columns capable of
supporting a scavenger or a reagent. Low back
pressures and the geometry of mold vessels ena-
ble simple and effective functionalization proce-
dures yielding columns for flow-through solid
phase synthesis methods. These features further
suggest the possibilities of connections of more
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
6733
columns in a row. Other chemistries of the column
material and means of pumping are currently
under investigation in our laboratories.
The authors thank the Ministry of Science, Technology
and Higher Education for a scholarship to Sebastijan
Kovačič and to Prof. Stanovnik and Mrs. Stipanovič
from the University of Ljubljana for CHN elemental
analyses. Containers for polymerization were kindly
supplied by BIA Separations, Ljubljana, Slovenia.
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DOI 10.1002/pola