Hydrogen bonding interactions in methacrylate monomers
and polymers
Marianela T. Lemon, Melissa S. Jones, Jeffrey W. Stansbury
Department of Craniofacial Biology, University of Colorado School of Dentistry, Aurora, Colorado 80045
Received 10 February 2006; revised 22 August 2006; accepted 8 February 2007
Published online 8 June 2007 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.a.31448
Abstract: It is well appreciated that hydrogen bonding
affects a variety of monomer and polymer properties. This
study focused on Bis-GMA and urethane dimethacrylate
(UDMA) to help elucidate how the strength and nature of
specific noncovalent interactions involved with these dif-
ferent functional dimethacrylate structures are expressed
in the monomers and polymers. Hydrogen bonding inter-
actions in monomers and comonomer mixtures as well as
in appropriate model compounds were examined by FT-IR
under ambient conditions, at elevated temperatures and in
dilution studies. The investigation of hydrogen bonding
extended to monomer viscosity, photopolymerization reac-
tion kinetics, and polymer mechanical properties. The
strength of hydrogen bonding was shown not only to be
greater for Bis-GMA compared with UDMA, but there is
also greater contribution from intermolecular interactions
INTRODUCTION
Several commonly used dimethacrylate monomers
include secondary functionality such as hydroxyl or
urethane groups. Hydrogens attached to oxygen or
nitrogen, depending on monomer structure, can
engage in intramolecular and/or intermolecular
hydrogen bonding interactions with similar groups
or with ether, carbonyl, and other electronegative
acceptor functionality. The strength of any specific
hydrogen bonding interaction generally increases
in relationship with the basicity of the lone pair
acceptor and the acidity of the hydrogen bond do-
nor. These interactions can affect monomer configu-
ration and mobility on the molecular level, which in
turn result in viscosity differences on the macro-
scopic scale of the bulk monomer. In comonomer
mixtures, intermolecular hydrogen bonding im-
proves compatibility in the monomeric and final
Correspondence to: J. W. Stansbury; e-mail: jeffrey.stansbury@
uchsc.edu
Contract grant sponsor: NIH/NIDCR; contract grant
number: DE14227
' 2007 Wiley Periodicals, Inc.
that enhance the hydrogen bonding effects. While UDMA-
based polymers reach significantly higher levels of conver-
sion compared with Bis-GMA materials, the stronger
hydrogen bonding reinforcement associated with Bis-GMA
appears to provide for comparable mechanical strength
properties. Depending on the hydrogen bond donor func-
tionality of a monomer as well as its neighboring func-
tional groups, overall monomer structure and comonomers
used, hydrogen bonding can favorably affect polymeriza-
tion reactivity and mechanical properties, even in materials
that form highly crosslinked polymeric networks. 2007
Wiley Periodicals, Inc. J Biomed Mater Res 83A: 734746,
2007
Key words: dental resins; dimethacrylates; hydrogen bond-
ing; kinetics; photopolymerization
polymerized states. Besides being associated with
the handling properties of a given monomer or mix-
ture of monomers, these mobility factors are respon-
sible in part for controlling polymerization kinetics
and ultimate conversion that can be achieved.1,2
Intermolecular hydrogen bonding interactions have
been shown to promote gelation at lower conver-
sion3 while photopolymerizations conducted at
elevated temperatures, which disrupt hydrogen
bonding, have been used to demonstrate the direct
positive relationship between hydrogen bonding and
reaction kinetics for hydroxyl-substituted acrylates.4
Separate works have focused on the complex rela-
tionships between polymerization reaction kinetics
and monomer structure including a series of ure-
thane monomethacrylates.57 In other prior studies
directed to dental composite restorative materials,
significant efforts have been made to develop lower
viscosity analogs of Bis-GMA or alternative mono-
mer structures by elimination of hydrogen bond do-
nor groups.810 In the polymeric state, hydrogen
bonding interactions can reinforce the three-dimen-
sional structure, which can involve either entangled
linear chains or covalently crosslinked networks,
to potentially provide enhanced glass transition
HYDROGEN BONDING INTERACTIONS IN METHACRYLATE MONOMERS AND POLYMERS
temperatures and mechanical properties. The polar
hydrogen bond donors also significantly affect the
surface wetting behavior of monomers and the
hydrophilic character associated with the corre-
sponding polymers. For dental monomers typically
based on dimethacrylates, OH groups, such as in
Bis-GMA, or NH groups, such as in urethane dime-
thacrylate (UDMA), can form hydrogen bonds with
ether or carbonyl functional groups as well as
among themselves (primarily for OH groups, since
direct NH


NH interactions involving urethanes
are minimal11). This along with the distribution of
intra- versus inter-molecular interactions controls the
behavior of the monomers and can also impact the
final polymer properties. The goals of this study are
to characterize the hydrogen bonding interactions in
common dental monomers and examine how these
interactions affect monomers, the polymerization
process, and final polymer function.
There are several approaches used here to identify
and evaluate the hydrogen bonding interactions
within conventional dimethacrylate dental mono-
mers. These involve the use of model compounds,
which can provide information on the specific func-
tional group-dependent hydrogen bonding interac-
tions present. In addition, thermal studies at a series
of elevated temperatures were conducted as were
solvent dilution studies, which were used to exam-
ine the concentration effect on monomer hydrogen
bonding. Mid-infrared (IR) spectroscopy was used
to characterize hydrogen bonding based on specific
OH, NH, and C O stretching absorption regions of
the spectra. Deconvolution of these peaks allows
the various sources of the hydrogen bonding con-
tributions to be isolated and studied with the aid
of information gained from the simpler model com-
pounds.
The strength of a specific hydrogen bond can be
inferred from the length of the OH or NH bond,
which is directly measured by the vibrational spec-
troscopic techniques used here. A stronger hydrogen
bonding interaction will result in a weaker funda-
mental OH or NH covalent bond, as indicated
by an absorbance at lower frequency and typically,
with greater intensity. There are many potential con-
formations associated with the approach of the
hydrogen bond donor and acceptor, whether this
involves a unimolecular (intramolecular) or a bi/
multi-molecular (intermolecular) process. A typical
hydrogen bonding interaction is transient with a life-
time on the order of 109 to 1012 s.12 Therefore, on
the time scale of the IR analysis, the distribution of
these conformational differences is averaged such
that only distinctly different donor/acceptor interac-
tions are provided from the spectral data. These rela-
tively strong, noncovalent interactions (generally 36
kcal/mol) influence monomer properties and the
735
same interactions amplified through summation
effects, can dramatically impact polymer properties.
EXPERIMENTAL
Materials
A variety of methacrylate monomers with different sec-
ondary functionalities were evaluated for their potential as
hydrogen bond donors and/or acceptors. All initiators,
monomers, and model compounds were used as received.
Dimethacrylate monomers
2,2-bis[p-(20 -hydroxy-30 -methacryloxypropoxy)phenyle-
ne]propane (Bis-GMA)a
1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-tri-
methylhexane (UDMA)a
ethoxylated bisphenol A dimethacrylate (EBDMA)a with
an average of 4.3 ethoxy groups per molecule
glycerol dimethacrylate (GDMA)b
neopentyl glycol dimethacrylate (NDMA)a
triethylene glycol dimethacrylate (TEGDMA)a
Monomethacrylate monomers
2-hydroxyethyl methacrylate (HEMA)a
2-hydroxypropyl methacrylate (HPMA)b (contains *20%
of the 2-hydroxy-1-methylethyl methacrylate isomer)
Model compounds
ethyl N-ethylcarbamate (EEC)b
isopropanol (IP)b
1-phenoxy-2-propanol (PP)b
a
Esstech, Essington, PA
b
Aldrich, Milwaukee, WI
Methods
Mid-IR spectroscopy (Nexus 670, Nicolet, Madison, WI)
was used to evaluate the hydrogen bonding interactions
of bulk, thin film specimens (about 1530 lm thickness)
between sodium chloride disks. Spectra were collected ei-
ther at ambient temperature (22.8 6 0.4)8C or at elevated
temperatures (37, 47, 57, or 678C) controlled by a cali-
brated temperature cell inserted into a horizontal sam-
pling accessory.13 Solution state IR spectra of monomers
and model compounds were obtained at varied dilution
concentrations (0.05, 0.1, or 0.2 mol/L) in carbon tetra-
chloride as a solvent with minimal hydrogen bonding
character. A variable pathlength liquid cell (International
Crystal Laboratories, Garfield, NJ) was used with a path-
length of either 75, 50, or 25 lm, respectively. The stretch-
ing frequencies of the OH, NH and C O absorptions in
Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a
736 LEMON, JONES, AND STANSBURY

mid-IR spectra were examined in detail, which included

deconvolution (PeakFit, SPSS, Chicago, IL). Selected
monomers and comonomer compositions were rendered
photocurable by incorporation of 2,2-dimethoxy-2-phenyl-
actophenone (DMPA, 0.2 wt %, Aldrich). Specimens (1.2-
mm thick by 12 mm diameter) in Teflon molds between
glass slides were placed in the horizontal accessory14 of
the IR at ambient temperature. Photopolymerization was
induced by irradiation with filtered UV light (320390
nm) from a 100 W mercury arc lamp (Novacure, EXFO,
Mississaugua, Ontario). The incident irradiance was 20
mW/cm2 as measured by radiometer (International Light,
Newburyport, MA) and the exposure interval was 5 min.
Real-time near-IR spectra were collected from four aver-
aged scans at 4 cm1 resolution, which provided a tempo-
ral resolution of 0.9 s. The methacrylate
CH2 first over-
tone absorption at about 6160 cm1 was used to monitor
the carboncarbon double concentration throughout the
polymerization process.15 The temperature-dependent vis-
cosity of various comonomer compositions (7:3 weight
ratios of base monomer to diluent comonomer) was meas-
ured with a viscometer (CAP2000, Brookfield, Middleboro,
MA) up to *508C. Polymer specimens (2 3 2 3 25 mm3)
for mechanical strength testing (n 8) were prepared in
stainless steel molds between glass slides by UV irradia-
tion. The three-point (10 mm span) flexural strength and
modulus of copolymers stored dry for 24 h were deter-
mined at a strain rate of 1 mm/min (Bionix II, MTS Sys-
tems, Eden Prairie, MN).

Figure 1. Deconvoluted IR spectra focused on the OH

RESULTS AND DISCUSSION (top) and NH (bottom) stretching absorptions of Bis-GMA
and UDMA, respectively.

Studies of hydrogen bonding in Bis-GMA

The deconvoluted OH and NH stretching region of
the IR spectra of Bis-GMA and UDMA, respectively
(Fig. 1), clearly show that there are multiple interac-
tions involved with the hydrogen bonding states of
these commonly used monomers. The studies of
bonding interactions involving the hydroxyl groups
of IP, PP, HEMA, HPMA, and GDMA, all of which
can serve as models for the hydroxyl portion of Bis-
GMA, provide some useful insights into the specific
assignments of the hydrogen bonding states. The OH
stretching region of the hydroxyl-containing mono-
mers and model compounds are presented in Figure 2.
In the simplest case, IP, which absorbs at the lowest
frequency of this series (OH mmax 3447 cm1), con-
tains only the hydroxyl functional group and there-
fore, can engage only in intermolecular OH


OH
hydrogen bonding. On deconvolution of the OH peak
of IP, it is evident that there are at least two constitu-
ent contributions, which can be assigned to singly
bonded dimer or to extended doubly bonded trimers
and higher oligomers (Fig. 3) that appear at higher
and lower frequency, respectively.16 The limited
steric shielding associated with the compact IP struc-
ture leads to significant proportions of doubly
bonded interactions which produce relatively strong
hydrogen bonding effects based on their extended na-
ture. The next strongest hydrogen bond, as deter-
mined by the position of the peak maximum is
observed for PP (OH mmax 3388 cm1) that mimics
the internal portion of the Bis-GMA structure. This
more structurally complex compound can engage in
intermolecular OH


OH hydrogen bonding along
with intra/intermolecular OH


ether interactions.
The OH stretch for PP also shows a clearly resolved
shoulder at higher frequency (m 3576 cm1), which
corresponds to the weak intramolecular hydrogen
bonding interaction with the aromatic ether. There is
less of the strongest doubly hydrogen bonded
OH


OH interaction compared with IP. This indicates
that if the intramolecular hydrogen bonding with the
ether activates the OH as a proton acceptor in bond-
ing with another OH (or ether), the resulting doubly
bonded complex is weaker than that formed exclu-
sively from extended OH


OH interactions. Weaker
interactions may be expected since the five-mem-
bered intramolecular cyclic structure imposes nonli-
nearity on the hydrogen bond geometry12 although
more complex coupled intra/intermolecular hydro-
gen bonding structures are possible.17

Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a

HYDROGEN BONDING INTERACTIONS IN METHACRYLATE MONOMERS AND POLYMERS
Figure 2. IR spectra of the OH stretching region for Bis-
GMA as well as related monomers and model compounds.
HEMA and HPMA were also evaluated as models
to simulate the external portion of the Bis-GMA
structure. The significantly lower frequency of the
OH stretching maxima of IP and PP relative to
HEMA and HPMA points to the weaker hydrogen
bond acceptor potential of an ester carbonyl com-
pared with a hydroxyl group. HPMA should be a
good model for Bis-GMA since it contains a mixture
of isomers favoring the secondary hydroxyl over the
primary hydroxyl in a ratio similar to the isomeric
mixture present in Bis-GMA.18 In these examples,
intra/intermolecular OH


O C bonding is com-
bined along with intermolecular OH


OH interac-
tions, which is an appropriate model for Bis-GMA
since no direct intramolecular OH


OH interactions
are possible due to the rigid structure of the core
group.2,19 The weak hydrogen bonding (higher fre-
quency) portion of the HEMA and HPMA OH
stretching absorptions closely approximate that of
Bis-GMA but HPMA and particularly HEMA, with a
more accessible primary hydroxyl group, have sig-
nificantly greater contributions from the stronger
doubly hydrogen bonding OH


OH interactions that
shift the peak maximum to lower frequencies (OH
mmax 3438 and 3437 cm1 for HPMA and HEMA,
respectively) compared with Bis-GMA (OH mmax
3461 cm1). With methacrylate ester groups flanking
Figure 3. Representative examples of singly (dimers) and doubly (linear and cylic trimers, tetramers, etc.) hydrogen
bonded interactions between hydroxyl groups or hydroxyl and carbonyl groups.
737
the central OH group, GDMA exhibits the weakest
overall hydrogen bond strength (OH mmax 3489
cm1). This final case provides evidence that the
intra/intermolecular OH


O C interactions that are
emphasized in this dimethacrylate structure are rela-
tively weak. The strong doubly bonded intermolecu-
lar OH


OH interactions in GDMA are apparently
minimized by the steric constraints imposed by the
two adjacent methacrylate groups.
Hydrogen bonding interactions are often exam-
ined through analysis of the carbonyl stretching
absorption since as hydrogen bond acceptors only,
the interactions tend to be simpler than those of the
OH or NH stretching and because the carbonyl IR
peak intensities are less influenced by hydrogen
bonding. The carbonyl absorptions can be deconvo-
luted reliably20 to demonstrate the presence of two
overlapping absorptions: a nonhydrogen bonded
O at about 1723 cm1 and a broader hydro-
(free) C
gen bonded C O peak at about 1703 cm1 (Fig. 4).
The peak areas of the two constituent peaks provide
an estimation of the relative contribution of the
OH


O C interactions to overall hydrogen bonding
(Table I). In Bis-GMA, the hydrogen bonded car-
bonyl peak is significantly greater than that of the
nonhydrogen bonded carbonyl. For comparison, the
carbonyl peaks of both HEMA and HPMA are split
nearly equally between hydrogen bonded and non-
bonded components while in GDMA, which repre-
sents the other extreme, free carbonyl is present in a
considerable excess. There is equivalent stoichiome-
tery between carbonyl and hydroxyl groups in Bis-
GMA, HEMA and HPMA while GDMA has twice as
many carbonyl groups, which undoubtedly affects
the proportion of bonded carbonyl present.
UDMA hydrogen bonding
For a separate study focused on photopolymeriza-
tion reaction kinetics, we previously prepared the
urethane monomethacrylates I and II (Fig. 5).5 In this
isomer pair, monomer I has a melting point of 288C
while a reversal of the urethane functionality in
monomer II increases the melting point to 43458C.
Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a
738 LEMON, JONES, AND STANSBURY

Figure 5. Structures of urethane monomethacrylate iso-

mers used as models for UDMA.

bonded states with a ratio of two carbonyls (ure-

Figure 4. IR spectra of the carbonyl stretching region for
Bis-GMA and related monomers.
The more central placement of the hydrogen bond-
ing HN group in monomer II may account for its
higher melting point. Monomer I is included in the
evaluation here as a simplified model for UDMA.
While UDMA presents complex hydrogen bonding
with multiple potential intra/intermolecular interac-
tions involving both ester and urethane carbonyl
groups, the wide use of polyurethanes has lead to a
significant number of prior studies on urethane-
based hydrogen bonding.11,21-24 An additional com-
plicating factor is that within the urethane function-
ality, the OC NH group adopts a planar form
to maximize resonance overlap. This means the NH
bond can be oriented either cis or trans with respect
to the adjacent C O group. The cis NH configura-
tion is favored since this puts the N-alkyl unit in the
lower energy trans orientation but the alternate con-
formation is not excluded.11 The methacrylate ester
and urethane carbonyl groups appear at similar
positions in the mid-IR21 and no attempt was made
to resolve these here. From the data in Table I and
the C O stretching spectra shown in Figure 6, the
mixed carbonyl peak in UDMA displays an approxi-
mately equivalent distribution of bonded and non-
thane and ester) for each NH in this structure.
Unlike hydroxyl groups where the OH can serve
effectively as both hydrogen bond donor and
acceptor, in urethanes, the nitrogen is not strongly
electronegative due to electron donation to the ure-
thane carbonyl. Therefore, the NH group is an inef-
fective hydrogen bond acceptor and essentially all
hydrogen bonding in the urethane-based monomers
involves NH


O C interactions or NH


ether and/
or NH


OH bonding.11 As shown in Figure 7, hydro-
gen bonding with the methacrylate ester carbonyl
involves formation of only a single bond whereas
the interaction between urethane functional groups
can form a more stable two-bond dimer structure.
The potential for extended oligomeric hydrogen
bonded structures is limited by the requirement that
the higher energy trans NH structures be adopted to
achieve this. Also, the cyclic dimer formed by ure-
thaneurethane bonding is particularly stable and
this likely limits the proportion of extended oligo-
meric bonded species. The weak hydrogen bonding
region of the carbonyl spectrum for monomer I
matches that of UDMA but UDMA has a slightly
higher proportion of stronger hydrogen bonding
interactions. In the EEC nonmethacrylate model,
which has an equal ratio of NH and C O groups
and exclusively involves intermolecular interactions,
the hydrogen bonded form of the carbonyl is present
in a fourfold excess compared with the contribution

TABLE I
Mid-IR Carbonyl Stretching Absorptions with
Deconvoluteda Constituent Peak Positions and Peak
Area Ratios
Free Bonded Bonded/
O mmax,
C Oa mmax,
C Oa mmax,
C O
Free C
Compound (cm1) (cm1) (cm1) Ratio
Bis-GMA 1718 1723 1705 1.62
HEMA 1720 1723 1702 1.08
HPMA 1720 1721 1704 0.86
GDMA 1720 1723 1702 0.52
UDMA 1721 1725 1703 1.07
Monomer I 1722 1725 1704 0.89 Figure 6. IR spectra of the carbonyl stretching region
EEC 1700 1726 1700 4.18 for UDMA and related urethane monomers and model
compounds.

Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a

HYDROGEN BONDING INTERACTIONS IN METHACRYLATE MONOMERS AND POLYMERS
Figure 7. Representative structures showing urethane hydrogen bonding interactions involving a single bonded dimer
with a methacrylate carbonyl (left), doubly bonded urethane-urethane dimer (center) and potential oligomers through
extended urethane bonding (right).
of the free urethane carbonyl. With the expectation
of efficient dimer formation in the exclusive ure-
thaneurethane hydrogen bonding interactions as-
sociated with EEC, the high proportion of bonded
carbonyl is not surprising. It is apparent that the
inclusion of competing ester and urethane carbonyl
groups as hydrogen bond acceptors in UDMA pro-
vides a restriction on the strength of these interac-
tions.
In the NH stretching region (Fig. 8), just as in the
carbonyl region, EEC demonstrates the strongest hy-
drogen bonding interactions (NH mmax 3338 cm1)
in this series. The NH stretch in UDMA has a mmax
3353 cm1, which is bracketed by that of monomer I
at higher frequency (mmax 3360 cm1) and mono-
mer II at lower frequency (mmax 3349 cm1). The
NH peak positions of the urethane monomethacry-
late isomers appear to indicate that intramolecular
hydrogen bonding between the urethane NH and
the methacrylate C O is not particularly significant
since the seven-membered cyclic structure associated
with II should be preferred compared with the nine-
membered counterpart required for I. If the intra-
molecular NH


O Cester interactions effectively
compete with the intermolecular NH


O Curethane
bonding, the NH peaks for I and II could be
expected in the reverse order to that observed
here. Therefore, in spite of the proximity of the
available methacrylate carbonyl, intermolecular
Figure 8. IR spectra of the NH stretching region for
UDMA and related urethane compounds.
739
NH hydrogen bonding with urethane and methac-
rylate carbonyls may be more prevalent since these
interactions can readily adopt the favorable linear
geometry.
The effect of water on OH and NH absorptions
was examined in GDMA and UDMA, respectively.
The addition of either 0.5 or 1.0 wt % of water to the
monomers resulted in single phase mixtures. For
both GDMA and UDMA, the position of the peak
maxima at 3489 and 3353 cm1, respectively, was
not affected by the presence of small amounts of
water. While the NH peak shape of UDMA was
only slightly altered by the addition of water (half
height peak broadening of only 0.3 and 6.7 cm1 for
0.5 and 1.0 wt % water, respectively, compared with
the unmodified monomer), the OH peak for GDMA
was significantly broadened (peak width at half
height increases of 9.1 and 39.3 cm1) with a clear
enhancement to a preexisting longer wavelength
shoulder at 3424 cm1 as water was added. These
results indicate that small differences in moisture
content in monomers should not alter interpretations
about hydrogen bonding based on positions of peak
maxima but clearly it can complicate more in depth
evaluations reliant on curve fitting. It also suggests
that at least for the monomer pair evaluated here, as
hydrogen bond donors, urethane groups interact less
with water than do hydroxyl groups, which would
lead to lower degrees of hydrophilicity associated
with urethane methacrylates compared with other-
wise structurally similar hydroxyl-substituted metha-
crylates.
Concentration dependent hydrogen bonding
For all samples of bulk monomer, only extremely
limited free OH or NH contributions to the overall
absorbance peaks were observed in the deconvo-
luted IR spectra. However, the percentage of OH
(for Bis-GMA, GDMA, HPMA and HEMA) and NH
(for UDMA and EEC) that is contributed by a non-
hydrogen bonded state was determined from the
deconvoluted spectra obtained at fixed levels of
monomer dilution in carbon tetrachloride, which
was selected as a minimally bonding solvent. The
partial IR spectra focused on the fundamental OH/
Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a
740
Figure 9. Concentration dependence of the IR stretching
peak maxima for OH or NH in selected monomers.
NH absorbances in Bis-GMA and UDMA as a func-
tion of monomer concentration are shown in Figure
9 and the data is summarized in Table II along with
results for other monomers and model compounds.
It is apparent that the free OH of Bis-GMA consists
of two bands that differ in intensity as concentration
is changed. This may be a result of the presence of
both primary and secondary OH groups where the
free OH of the latter would be expected at lower fre-
quency.16 Similar results are observed in the spectra
of GDMA, which also provides a mixture of isomers,
while HEMA and HPMA show a single free OH
peak. Dilution of the monomers in a nonpolar sol-
vent disrupts the intermolecular hydrogen bonds
with limited impact on the intramolecular interac-
tions. Therefore, one way to examine the results is to
follow the change in proportion of the free OH or
NH with dilution. The 2.9-fold increase in free OH
seen for Bis-GMA between 0.2 and 0.05M indicates a
modestly greater level of overall intermolecular
hydrogen bonding compared with the 2.6-fold
increase obtained for UDMA. By this measure,
HEMA, with a 4-fold increase in free OH over the
dilution range used here, appears to have the largest
percentage of intermolecular hydrogen bonding
interactions, which may be justified by its accessible
primary hydroxyl group. EEC provided the greatest
Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a
LEMON, JONES, AND STANSBURY
increase in proportion of free NH with dilution,
which can be attributed to the lack of any intramo-
lecular hydrogen bonding.
Alternatively, changes in hydrogen bonding as a
function of dilution can be monitored by shifts in
the peak maxima of the bonded OH and NH stretch-
ing absorptions. By this approach, the OH peak max-
ima change by greater amounts than do the urethane
NH peaks as concentration is decreased (Table II).
The OH peak shift dilution response for HEMA
exceeds that of Bis-GMA but the largest effect was
noted for PP. The shift to higher frequency as con-
centration is reduced for OH-containing structures
provides evidence that the strongest hydrogen bonds
involve considerable intermolecular interactions.
Conversely, the consistency observed for the NH
peak maxima with dilution is an indication that
intramolecular hydrogen bonding plays a signifi-
cant role in both weak and strong interactions. The
differential between the free OH/NH peak position
and the position of the bonded peak maxima was
also evaluated (Table II). According to this, all the
hydroxyl-based hydrogen bonding interactions are
stronger than those associated with the urethanes.
Thermal studies of hydrogen bonding in Bis-GMA
and UDMA
The OH or NH peak maxima from IR spectra of
neat methacrylate monomers were obtained between
room temperature and 678C as a means to probe the
relative strength of hydrogen bonding interactions.
The noncovalent interactions associated with hydro-
gen bonds in the monomeric state can be disrupted
by an increase in temperature. While heating
impacts intramolecular hydrogen bonding interac-
tions as higher energy conformations become more
accessible, as with dilution, the preferential effects
are expected on intermolecular hydrogen bonds due
to the progressive decrease in density that accompa-
nies increased temperature. To simplify the analysis,
only the peak maxima and the general peak shapes
were evaluated here. The increase in temperature
has a significant effect on the shape and peak max-
ima of the OH absorption in Bis-GMA but the ther-
mal impact on the NH absorption in UDMA is more
limited. As expected, the peak maxima shift to
higher frequency as temperature is increased. Over
the temperature range probed here, the shift in max-
ima with respect to temperature is linear for both
Bis-GMA and UDMA (Fig. 10); however, the extent
of the thermal effect is 50% greater for Bis-GMA.
The thermal IR study extended to HEMA and
GDMA, which showed the greatest and least thermal
sensitivity, respectively. This pattern agrees with
the dilution dependence of the OH peak noted
HYDROGEN BONDING INTERACTIONS IN METHACRYLATE MONOMERS AND POLYMERS 741

TABLE II
IR Analysis of the Hydrogen Bonding Concentration Dependence Based on OH/NH Stretching Vibration
Hydrogen Bond
Bonded to Free Hydrogen Bonded Lengthening of
Monomer/ Free OH/NH OH/NH Ratio, OH/NH OH/NH
Concentration mmax, (cm1) (Peak Area) mmax, (cm1) Stretch, (%)a

Bis-GMA 3610, 3589 3461a 4.1

0.2M 11.3 3486
0.1M 6.6 3491
0.05M 3.9 3495
PP 3619 3388b 6.4
0.2M 3.6 3482
0.1M 2.2 3490
0.05M 1.5 3503
HEMA 3627 3437b 5.2
0.2M 10.1 3506
0.1M 4.1 3515
0.05M 2.5 3518
HPMA 3619 3438b 5.0
0.2M 3.5 3502
0.1M 2.2 3509
0.05M 1.5 3513
GDMA 3623, 3600 3489b 3.7
0.2M 11.2 3506
0.1M 6.9 3509
0.05M 3.9 3512
UDMA 3462 3353b 3.1
0.2M 4.6 3377
0.1M 2.8 3377
0.05M 1.8 3377
EEC 3461 3338b 3.6
0.2M 1.7 3367
0.1M 0.8 3370
0.05M 0.3 3372
a
Difference between peak positions of free OH/NH and neat monomer mmax (based on highest frequency in case of mul-
tiple peaks).
b
Neat monomer.

previously and the behavior can be explained by
more pronounced intramolecular hydrogen bonding
between the OH and the adjacent methacrylate car-
bonyl groups in GDMA compared with greater pro-
portions of doubly bonded primary OH groups in
HEMA. The shifts in OH or NH peak maxima with
temperature for the comonomer mixtures are shown
in Table III. Here the OH absorption maxima for Bis-
GMA-based compositions display the greatest tem-
perature sensitivity with the addition of GDMA as a
diluent comonomer with hydrogen bond donor/
acceptor capability producing the most profound
effect even though GDMA alone showed very lim-
ited thermal effect on the OH hydrogen bond. This
provides evidence of strong intermolecular interac-
tions associated specifically with Bis-GMA. The
reduced thermal response of hydrogen bonding of
NH (and OH with GDMA comonomer) in UDMA
resins points to weaker intermolecular hydrogen
bonding interactions. Despite the limited bonding
potential in the EBDMA/GDMA comonomer combi-
nation, the thermal effect on hydrogen bonding
slightly exceeded that of the UDMA materials.
Monomer and resin viscosity
Viscosity is the internal resistance of a fluid to
flow. Intermolecular hydrogen bonding interactions
raise monomer viscosity by an increase in the appa-
rent molecular weight of monomers and promotion
of greater cohesive energy. The dihydroxy and diu-
rethane structures of Bis-GMA and UDMA mean
that the effects of hydrogen bonding can be
extended through continuously reforming local
physical network structures. The extent of the tran-
sient network effect would be directly proportional
to the average strength of the interaction and the
degree to which intermolecular interactions contrib-
ute to the overall hydrogen bonding. Among com-
monly used dimethacrylate dental monomers, Bis-
GMA has the highest viscosity by well over an order
of magnitude. Depending on the degree of oligome-
rization of the aromatic core, the viscosity of Bis-
GMA can vary widely over a span from <500 Pa s
to >1200 Pa s. The dramatically higher viscosity of
Bis-GMA relative to other hydrogen bonding mono-

Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a

742
Figure 10. Effect of temperature on the IR stretching peak maxima for OH or NH in Bis-GMA (top), UDMA (center) and
plotted for selected monomers (bottom).
mers appears to result primarily from the rigid core
group structure that excludes direct intramolecular
OH


OH interactions and the promotion of mainly
intermolecular OH


OC interactions.
For comonomer mixtures of the various combina-
tions of hydrogen bonding and nonhydrogen bond-
ing methacrylates, the temperature dependent
Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a
LEMON, JONES, AND STANSBURY
changes in resin viscosity were evaluated as a com-
plement to the thermal IR studies. All the Bis-GMA-
based resins showed the highest ambient viscosities
as well as the steepest decreases in viscosity with
increased temperature (Fig. 11 and Table III). The
UDMA resins were intermediate in initial viscosity
but the temperature sensitivity of viscosity for these
HYDROGEN BONDING INTERACTIONS IN METHACRYLATE MONOMERS AND POLYMERS 743

TABLE III
Thermal Effects on Comonomer Hydrogen Bonding and Viscosity
OH/NH mmax Change
Hydrogen Bond with Temperature Linear Viscosity Slope 3 102
Comonomersa Donor, Base/Diluent (37678C) Regression r2 (h) (Pa s)b Dh /DT, (Pa s/8C)

Bis-GMA/GDMA / 0.73 0.98 5.51 5.42

Bis-GMA/NDMA / 0.41 0.96 1.48 5.56
Bis-GMA/TEGDMA / 0.98 4.04
UDMA/GDMA / 0.22 0.99 0.52 3.45
UDMA/NDMA / 0.19 0.98 0.27 3.52
UDMA/TEGDMA / 0.19 3.00
EBDMA/GDMA / 0.26 0.92 0.18 3.20
EBDMA/NDMA / 0.08 2.94
a
All compositions 7:3 weight ratios.
b
Viscosity measured at 308C.

resins was only slightly greater than that of the low
viscosity comonomer pairs obtained with EBDMA
as the base monomer. The entirely nonhydrogen
bonding resin composed of EBDMA/NDMA pro-
vided the lowest overall viscosity and the least tem-
perature dependence. The viscosity behavior of this
resin can be considered a baseline level to which
hydrogen bonding contributes increasing thermal
sensitivity that is directly related to the strength of
the intermolecular hydrogen bonding interactions.
The contribution of the diluent monomer, either
GDMA as a hydrogen bond donor or NDMA which
lacks this capability, produced clear viscosity differ-
ences in the resins, but only minor alterations in the
thermal sensitivity. The only resin pair showing a
significant difference in thermal sensitivity based on
the diluent monomer used was the EBDMA resins.
This demonstrates that the bulk of the hydrogen
bonding interactions are linked to the presence of
Bis-GMA or UDMA as the primary hydrogen bond
donors. The dominance of the hydrogen bonding
effects of the base monomers is also evident since
the 7:3 weight ratios of comonomers used here rep-
resent molar ratios of GDMA and NDMA ranging
between 48 and 52%. The data in Figure 11 and Ta-
ble III also show that at equivalent levels of dilution,
TEGDMA is a particularly effective diluent comono-
mer with Bis-GMA or UDMA. In spite of the two
ether linkages and two methacrylate ester carbonyl
groups in TEGDMA, which can act as hydrogen
bond acceptors, TEGDMA promotes lower viscosity
and thermal sensitivity of viscosity compared with
NDMA.
Photopolymerization reaction kinetics
The results of the homopolymerization and co-
polymerization reaction studies were evaluated with
a view toward how hydrogen bonding and viscosity
affect polymerization kinetics. Within the forming
polymer, the transient intermolecular hydrogen
bonding interactions, which are located exclusively
on the crosslink and pendant group segments for

Figure 11. Thermal effects on the viscosity of comonomer mixtures (7:3 weight ratio compositions).

Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a

744 LEMON, JONES, AND STANSBURY

TABLE IV were no significant effects on reactivity related to

Photopolymerization Kinetics of Monomers whether the diluent comonomer used included a
and Comonomer Mixtures
hydrogen bond donor group. In terms of immediate
Normalized conversion limits obtained, in every case, the use of
Monomer/ Rate Immediate the lower viscosity NDMA diluent resulted in higher
Comonomer Maximuma, (s1) Conversionb, (%)
conversion compared with the hydrogen bonding
Bis-GMA 0.003 30.2 GDMA diluent. The Bis-GMA copolymers showed sig-
UDMA 0.087 56.9 nificant conversion limitations, which implies reduced
EBDMA 0.082 63.1 reactivity efficiency for Bis-GMA compared with
GDMA 0.032 51.8
NDMA 0.021 54.7 UDMA or EBDMA as free monomer25 but probably
Bis-GMA/GDMA 0.064 6 0.011 45.0 6 1.3 even more so as pendant groups utilized in crosslink
Bis-GMA/NDMA 0.059 6 0.010 48.4 6 0.4 formation.
UDMA/GDMA 0.076 6 0.001 56.5 6 0.4
UDMA/NDMA 0.074 6 0.008 59.0 6 0.6
EBDMA/GDMA 0.050 6 0.004 58.8 6 0.3
Hydrogen bonding in polymers
EBDMA/NDMA 0.050 6 0.005 60.8 6 0.6
a
Rate maximum/(1-conversion at rate maximum). The work of Lee et al. includes a discussion of the
b
Conversion value at 5 min.
real time analysis of hydrogen bonding during the
photopolymerization process and provides evidence
of hydrogen bond strengthening during polymeriza-
these dimethacrylate monomers, can cumulatively tion.4 A separate study follows hydrogen bonding
raise the system viscosity and allow autoacceleration interactions in thermal polymerizations of Bis-GMA,
to occur at lower conversion than in the absence of which were found to remain relatively constant up
hydrogen bonding.4 Among the homopolymers, to moderate levels of conversion and then decrease
UDMA and EBDMA produced the highest reaction at high conversion.26 Because of the nonisothermal
rates after normalization by the conversion at the conditions associated with the photocuring opera-
rate maximum (Table IV). This was followed by tions used here, only the static spectra of selected
moderate reaction rates for GDMA and NDMA with monomer/polymer pairs were examined. The hydro-
Bis-GMA having by far the lowest rate. Considering gen bond acceptor capabilities of a saturated car-
the ambient temperature monomer viscosities of Bis- bonyl may be modestly increased compared with
GMA, UDMA, EBDMA, GDMA, and NDMA are that of the unsaturated methacrylate ester. This
*850, 13, 2, 0.1, and 0.02 Pa s, respectively, with the along with the densification that accompanies poly-
exception of Bis-GMA; this order of reactivity paral- merization would favor an increase in hydrogen
lels the decrease in monomer viscosity. While factors bonding potential as polymerization occurs. How-
other than monomer viscosity affect the reaction ever, reduced mobility could negatively affect hydro-
kinetics, an optimal level of initial viscosity exists gen bonding ability. For the photocured copolymer of
that permits immediate onset of autoacceleration Bis-GMA/NDMA, the OH absorption at 3490 cm1
while monomer diffusion rates still remain high. The showed no change in the peak maximum compared
extremely high viscosity of Bis-GMA is clearly with the comonomer spectrum and only a slight
beyond this optimum viscosity range and both ter- increase in a longer wavelength contribution, which
mination and propagation processes are significantly indicates marginally enhanced hydrogen bonding in
mobility-restricted from the outset. The Bis-GMA the polymer. The OH region of the IR spectrum
homopolymerization yielded the lowest immediate from the polymerized Bis-GMA/GDMA mixture
conversion value while the lowest viscosity mono- showed essentially no change in either peak position
mers, GDMA and NDMA, gave intermediate limit- or shape relative to the monomer mixture. The NH
ing conversion. The higher reaction rates associated stretching absorption for UDMA/NDMA produced
with the UDMA and EBDMA polymerizations a shift of 6 cm1 toward shorter wavelength after
allows access to higher levels of conversion in spite polymerization, which indicates weakened hydrogen
of the higher initial monomer viscosities. bonding compared with the monomer mixture. The
In the two component mixtures, the reactivity combined OH/NH absorption in the UDMA/
decreased in the order of UDMA comonomers > Bis- GDMA formulation also shows a similar shift of 4
GMA comonomers > EBDMA comonomers. While the cm1 upon polymerization. This trend of modest
comonomer combinations containing either UDMA or weakening of hydrogen bonding in UDMA-contain-
EBDMA were less reactive than the corresponding ing polymers compared with the monomeric state
homopolymerizations of these monomers, the Bis- extended to UDMA/TEGDMA resins while the Bis-
GMA-based mixtures showed a substantial synergy in GMA/TEGDMA OH peak maximum was not
reactivity relative to the individual monomers. There affected by polymerization.

Journal of Biomedical Materials Research Part A DOI 10.1002/jbm.a

HYDROGEN BONDING INTERACTIONS IN METHACRYLATE MONOMERS AND POLYMERS
TABLE V
Mechanical Strength Properties of Dimethacrylate
Copolymers
Flexural Flexural
Comonomers Modulus, (MPa) Strength, (MPa)
Bis-GMA/GDMA 3654 6 148a 112 6 11a
Bis-GMA/NDMA 2860 6 92b 91 6 12a,b
UDMA/GDMA 3247 6 86c 111 6 21a
UDMA/NDMA 2737 6 53b,d 113 6 6a
EBDMA/GDMA 2520 6 88e 98 6 15a,b
EBDMA/NDMA 2116 6 86f 77 6 10b
Letters designate statistically significant differences
among groups following one way ANOVA with Tukey
pairwise multiple comparison test (p < 0.05).
The influence of hydrogen bonding in the polymer
state also included an assessment of polymer me-
chanical properties. Photocured specimens of the
comonomer series that combine various bonding and
nonbonding pairs were subjected to three-point bend
testing to failure. For each base monomer, the inclu-
sion of GDMA as a diluent comonomer capable of
contributing to hydrogen bonding resulted in a sig-
nificant increase in polymer flexural modulus com-
pared with use of NDMA as the diluent (Table V).
The largest relative change in polymer modulus due
to diluent monomer selection was observed with
EBDMA where GDMA represented the only hydro-
gen bond donor present. For the compositions
including GDMA as diluent, the modulus values
were in the order of Bis-GMA > UDMA > EBDMA
whereas with NDMA as diluent, Bis-GMA &
UDMA > EBDMA. Flexural strength results showed
a similar trend related to the choice of diluent; how-
ever, because of greater variability in the data, only
the EBDMA-based compositions produced a clear
statistically significant difference in favor of the
hydrogen bonding diluent. The results demonstrate
that hydrogen bonding interactions serve to reinforce
the mechanical strength properties of the crosslinked
polymer systems. Strong hydrogen bonding in Bis-
GMA resins apparently provides polymers with
good mechanical properties even in cases of rela-
tively low conversion and potentially inefficient
crosslinking associated with Bis-GMA.
CONCLUSIONS
Despite its bulky, rigid structure, Bis-GMA, either
alone or in comonomer mixtures, engages in strong
hydrogen bonding interactions that have a large
intermolecular component. This accounts for the
very high monomer viscosity and contributes to the
formation of polymers with good mechanical
strength where the hydrogen bonding reinforcement
745
is effectively retained. UDMA hydrogen bonding is
weaker and displays greater intramolecular charac-
ter. Polymerization of UDMA materials appears to
modestly disrupt its hydrogen bonding interactions.
In light of this, the comparable mechanical strength
of UDMA-containing polymers relative to those
based on Bis-GMA is probably the result of more ef-
ficient crosslinking involving the flexible UDMA
structure. Viscosity effects can dramatically alter po-
lymerization reactivity; however, in copolymeriza-
tions here, the increase in viscosity related to the use
of the hydrogen bonding diluent monomer produced
a negligible effect on reaction rate and modestly
decreased the final conversion achieved. It is difficult
to generalize hydrogen bonding effects since specific
structural differences of OH or NH functionalized
monomers as well as comonomer combinations used
can significantly alter the nature of hydrogen bond-
ing interactions and their ultimate impact on mono-
mer and polymer properties.
The authors thank Esstech for donation of many of the
monomers used in this study.
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