Designed Monomers and Polymers, Vol. 4, No. 4, pp.

301 314 (2001)

VSP 2001.

Investigations on the structure of poly(dimethacrylate)s

IZABELA BARSZCZEWSKA-RYBAREK 1 , ANNA KORYTKOWSKA 1;2
and MIROS AW GIBAS 1;
1 Department

of Physical Chemistry and Technology of Polymers, Silesian University of Technology,

ul. M. Strzody 9, 44-100 Gliwice, Poland
2 Institute of Coal Chemistry, Polish Academy of Sciences, ul. Sowinskiego 5, 44-102 Gliwice,
Poland

AbstractTwo series of urethane dimethacrylates were synthesized from monomethacrylates of

oligoethylene glycols and aromatic diisocyanates. The formation of associated monomer molecules
in solution was evaluated quantitatively by 1 H-NMR spectroscopy. The monomers were polymerized
free radically to form crosslinked polymers. The conversion of double bonds was determined with
the aid of FT-IR spectroscopy. The polymers were examined by dynamic mechanical thermal
analysis (DMTA) to obtain values of the glass transition temperature and storage modulus. The
latter enabled the network parameters for individual polymers to be evaluated. On the basis of
the experimental results, relationships between the crosslink density and the network parameter in
poly(dimethacrylate)s are discussed.
Keywords: Poly(urethane dimethacrylate); network parameter; crosslink density; DMTA; FT-IR
spectroscopy.

1. INTRODUCTION

We have previously reported the results of our experiments performed by using dynamic mechanical thermal analysis (DMTA) on the cross-linked polymers derived
from a series of aliphatic urethane dimethacrylates [1].
The monomers were synthesized from monomethacrylates of oligoethylen e glycols (OEGMMA) having one to four oxyethylene units and aliphatic diisocyanates,
i.e. hexamethylene-1,6-diisocyanat e (HMDI), 2,2,4(2,4,4)-trimethylhexyl-1,6-diiso cyanate (TMDI), and isophorone diisocyanate (IPDI). Both the monomers and the
corresponding polymers were thought to be model ones when investigating the
structure and properties of methacrylate-based dental restorative materials.

To whom correspondence should be addressed. E-mail: gibas@zeus.polsl.gliwice.pl

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Investigations on the structure of poly(dimethacrylate)s

For poly(dimethacrylate)s , we have proposed the following formulae relating the

cross-link density (q) to the conversion of double bonds ():

qD

2 1
:

(1)

Knowledge of q in ideal cross-linked systems allows the determination of the

network parameter (Mc ), which is the number-average molecular weight between
two cross-links [2], i.e. the molecular weight per cross-linked unit [3]:

Mc D

MW
;
q

(2)

where MW molecular weight of a repeating unit, here that of a monomer.

Since the conversion of double bonds in cured dental restorative materials is
known to range from 55 to 75% [4], we could assume some intermediate, arbitrary
value of D 2=3, yielding, according to equation (1), a value of q D 1=2.
In a rst approach, we could predict on this basis that the network parameter
values in poly(dimethacrylate)s should be approximately twice as large as the
molecular weight of the corresponding monomers, assuming equation (2) to be
valid. However, the experimental values of Mc estimated directly by DMTA for
the model poly(dimethacrylate)s in most cases appeared to be either comparable to
MW or even smaller [1]. We suggested this nding to be a result of intermolecular
interactions between the pendant chains and the cross-links involvin g urethane
linkages, which could be recognized by DMTA as additional branch points.
1
H-NMR experiments on the monomers in solution con rmed the formation of
associated molecules based on similar interactions. Nevertheless, we can not
exclude that simply non-ideality of poly(dimethacrylate ) network has an essential
effect on the disagreements observed; more experimental data is needed to elucidate
this problem.
In this paper, we report on our efforts to achieve a deeper look at the structure of
poly(dimethacrylate)s . The model series of urethane dimethacrylate monomers was
synthesized from monomethacrylates of oligoethylen e glycols (OEGMMA) and
aromatic diisocyanates : tolylene-2,4-diisocyanat e (TDI) and 4,40 -methylenebis(phenyl isocyanate ) (MDI), having the structures shown in Scheme 1.
Both the monomers given above and the resulting polymers have aromatic
structural units, thus enabling the determination of the conversion of double bonds
by use of IR spectroscopy. On this basis, we could expect to nd some closer
relationship s between the cross-link density and experimental values of the network
parameter.

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303

Scheme 1. Structure of monomers.

2. EXPERIMENTAL

2.1. Materials
HEMA (2-hydroxyethy l methacrylate, Sigma), TDI (tolylene-2,4-diisocyanate ,
98%, Aldrich), DBTDL (dibutyltin dilaurate, Fluka), and HQME (hydroquinone
monomethyl ether, Fluka) were used as received.
MDI [4,40 -methylenebis(pheny l isocyanate), MERCK] was distilled under vacuum to yield a product containing 88% of the 4,40 - and 12% of the 2,40 -isomer,
as determined by 1 H-NMR. Potassium carbonate (anhydrous, POCh) was dried for
a few hours before use at 120 C. BPO (benzoyl peroxide, POCh) was puri ed by
dissolvin g in chloroform and subsequent precipitation with methyl alcohol.
Methylene chloride (POCh) was dried over anhydrous sodium sulphate.
2.2. Syntheses of the monomethacrylates
Di-, tri-, and tetra-ethylene glycol monomethacrylates (DEGMMA, TEGMMA, and
TTEGMMA, respectively ) were prepared in a similar way to the method described
earlier, i.e. via transesteri cation of oligoethylen e glycols with methyl methacrylate,
or, alternatively, with the respective dimethacrylates [1, 5].
The monomethacrylates were separated from the reaction mixtures by extractions,
rst with water and then with chloroform, to obtain crude products, which were

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Investigations on the structure of poly(dimethacrylate)s

then puri ed by distillatio n under vacuum. Purity of nal products was con rmed
by 1 H-NMR.
2.3. Syntheses of the dicarbamates
2.3.1. Bis-(5-methyl-4-oxo-3-oxa-5-hexenyloxy)-N, N0 -tolylene-2,4 dicarbamate
(HEMA/TDI, C21 H26 N2 O8 ). A 50% w/w solution of HEMA (26.0 g, 0.2 mol)
admixed with DBTDL (13 mg, 0.03% w/w, the catalyst) and HQME (22 mg,
500 ppm, the inhibitor ) in methylene chloride was heated to 40 C in a three-neck
ask equipped with a mechanical stirrer, a thermometer, and a dropping funnel.
Later, a 50% solution of TDI (17.4 g, 0.1 mol) in methylene chloride was added
dropwise for 1 h, while maintaining the temperature at 50 C. Stirring was continued for 3 h. After evaporation of the methylene chloride, the mixture was left to
stand overnight in a drying oven at 40 C. The product appeared to be a white solid
melting at 86 C, as determined by DSC.
The above compound is known; a similar preparative procedure has been reported,
the purity being proved by FT-IR measurements [6]. We con rmed the formation
of dicarbamate by 1 H-NMR. Here, two broadened singlets at D 6:95 and
7.76 ppm, each of the intensity corresponding to 1H, can be assigned to NH protons
neighbourin g C(2) and C(4) of the 2,4-tolylene ring. The signals of the aromatic
protons are shifted with respect to the initial TDI: H(3) from D 6:76 ppm to
D 6:56 ppm, H(5) from D 6:82 ppm to D 7:24 ppm, and H(6) from
D 7:10 ppm to D 7:08 ppm. For both H(3) and H(5), a distinct broadening
was observed due to long-range spinspin coupling with neighbourin g NH protons.
Other evidence for the formation of the product is the collapse of the oxyethylene
signals to a broadened singlet at D 4:4 ppm (HEMA has two triplets at D 4:29
and 3.87 ppm). The methyl group of TDI gives a signal at D 2:20 ppm,
whereas the methacrylic protons exhibit the same chemical shifts as those for the
monomethacrylates.
2.3.2. Bis-(8-methyl-7-oxo-3,6-dioxa-8-nonenyloxy)-N, N0 -tolylene-2,4 dicarbamate (DEGMMA/TDI, C25 H34 N2 O10 ). The synthesis was performed in an analogous
way to that of HEMA/TDI, starting from 19.5 g (0.11 mol) of DEGMMA and 9.6 g
(0.055 mol) of TDI in the presence of 9 mg of DBTDL and 15 mg of HQME. The
product appeared to be a viscous, transparent, and colourless resin.
The 1 H-NMR spectrum differs from that of HEMA/TDI in the oxyethylene region.
Four narrow multiplets of equal intensities , corresponding to 4H each, were visible
and were assigned as follows to four methylene groups adjacent to the ester bond
at D 4:31, the urethane bond at D 4:21, and the ether oxygen at D 3:77 and
3.70 ppm.
2.3.3. Bis-(11-methyl-10-oxo-3,6,9-trioxa-11-dodecenyloxy)-N, N0 -tolylene-2,4 dicarbamate (TEGMMA/TDI, C29 H42 N2 O12 ). The synthesis was performed in an

I. Barszczewska-Rybarek et al.

305

analogous way, starting from 39.7 g (0.18 mol) of TEGMMA and 15.7 g (0.09 mol)
of TDI in the presence of 17 mg of DBTDL and 28 mg of HQME. The product was
a resin similar to DEGMMA/TDI, but less viscous.
The 1 H-NMR spectrum of the product, in comparison to that of DEGMMA/TDI,
contained an additional signal from the central oxyethylene unit at D 3:70 ppm
(s, 8H).
2.3.4. Bis-(14-methyl-13-oxo-3,6,9,12-tetraoxa-14-pentadecenyloxy)-N, N0 -tolylene-2,4 dicarbamate (TTEGMMA/TDI, C33 H50 N2 O14 ). The synthesis was performed in an analogous way, starting from 45.9 g (0.17 mol) of TTEGMMA and
14.8 g (0.085 mol) of TDI in the presence of 18 mg of DBTDL and 30 mg of HQME.
The product was a colourless, viscous liquid.
The 1 H-NMR spectrum of the product was the same as that for TEGMMA/TDI,
except for the singlet of the central oxyethylene units, which has an intensity
corresponding to 16H.
2.3.5. Bis-(5-methyl-4-oxo-3-oxa-5-hexenyloxy)-N, N0 -diphenylmethane-4,40 dicarbamate (HEMA/MDI, C27 H30 N2 O8 ). The synthesis was performed in an analogous way to that of HEMA/TDI, starting from 26.0 g (0.2 mol) of HEMA and
25.0 g (0.1 mol) of MDI in the presence of 15 mg of DBTDL and 26 mg of HQME.
The product appeared to be a white solid melting at 89 93 C (DSC).
The formation of dicarbamate was con rmed by 1 H-NMR. A broadened singlet at
D 6:97 ppm of intensity corresponding to 2H can be assigned to the NH protons.
The diisocyanate core gives a singlet of methylene groups at D 3:87 ppm (2H) and
two doublets (4H each) of aromatic protons at D 7:08 and 7.30 ppm (in the initial
MDI, they are located on the high- eld side, at D 6:97 and 7.07, respectively).
The broadened one (due to the spinspin coupling with NH) may be assigned to
H(3, 5, 30 , 50 ).
The oxyethylene and methacrylic protons exhibit the same chemical shifts as
HEMA/TDI.
2.3.6. Bis-(8-methyl-7-oxo-3,6-dioxa-8-nonenyloxy)-N, N0 -diphenylmethane-4,40
dicarbamate (DEGMMA/MDI, C31 H38 N2 O10 ). The synthesis was performed in an
analogous way to that of HEMA/MDI, starting from 19.1 g (0.11 mol) of DEGMMA and 13.8 g (0.055 mol) of MDI in the presence of 10 mg of DBTDL and
16 mg of HQME. The product appeared to be a viscous, transparent, light yellow
resin.
The 1 H-NMR spectrum of the product differed from that of HEMA/MDI in the
oxyethylene region in the same way as DEGMMA/TDI with respect to HEMA/TDI.
2.3.7. Bis-(11-methyl-10-oxo-3,6,9-trioxa-11-dodecenyloxy)-N, N0 -diphenylmethane-4,4 0 dicarbamate (TEGMMA/MDI, C35 H46 N2 O12 ). The synthesis was performed in an analogous way starting from 34.9 g (0.16 mol) of TEGMMA and

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Investigations on the structure of poly(dimethacrylate)s

19.2 g (0.08 mol) of MDI in the presence of 16 mg of DBTDL and 33 mg of HQME.

The product was a resin similar to DEGMMA/MDI, but less viscous.
The 1 H-NMR spectrum of the product, in comparison to that of DEGMMA/MDI,
contained an additional signal from the central oxyethylene unit at D 3:70 ppm
(s, 8H).
2.3.8. Bis-(14-methyl-13-oxo-3,6,9,12-tetraoxa-14-pentadecenyloxy)-N, N0 -diphenylmethane dicarbamate (TTEGMMA/MDI, C39 H54 N2 O14 ). The synthesis was
performed in an analogous way starting from 45.6 g (0.17 mol) of TTEGMMA
and 21.3 g (0.085 mol) of MDI in the presence of 20 mg of DBTDL. The product
was a dense, light yellow liquid.
The 1 H-NMR spectrum of the product was the same as that for TEGMMA/MDI,
except for the singlet of the central oxyethylene units, which has an intensity
corresponding to 16H.
2.4. Differential scanning calorimetry (DSC)
The calorimetric measurements were carried out on a DSC 2010 apparatus (TA
Instruments). Samples weighing approximately 2 mg each were heated from 20 to
250 C under nitrogen with a heating rate of 10 K/min. The recorded thermograms
of some of the obtained dicarbamates depicted the melting temperatures.
2.5. NMR measurements
1

H-NMR spectra were recorded with the aid of a UNITY/INOVA 300 MHz (Varian)
spectrometer, using CDCl3 as the solvent and TMS as the internal reference.
2.6. Determination of associatio n constants
The association constants (Kass ) of the formation of associated molecules were
determined by 1 H-NMR in CDCl3 , using the BenesiHildebrand equation [7], for
concentrations ranging from 2.08 to 0.001 mol/dm 3 :
1
1
1
1
1
;
D

C
1obs
Kass 1ass [c] 1ass

(3)

where Kass is the association constant, c is the concentration (in mol/dm3 ), 1obs D
obs free , 1ass D ass free , obs is the observed chemical shift of an NH
proton, free is the chemical shift of an NH proton obtained by approximation of
obs to in nite dilution, and ass is the chemical shift of an NH proton obtained by
approximation of obs to in nite concentration.
2.7. Polymerization
The monomers were mixed with 1% by weight of BPO and polymerized in Petri
dishes placed in a drying oven under nitrogen, raising the temperature gradually
from 50 to 90 C over 24 h.

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307

2.8. Dynamic mechanical thermal analysis (DMTA)

DMTA measurements were performed on 2 5 50 mm samples, using a Polymer
Laboratories MK II apparatus at a frequency of 1 Hz. Tg was determined by the
maximum value of the tan vs. T plot, whereas E 0 was obtained from the rubbery
plateau value of the modulus.
Theoretical values of the network parameter Mc were calculated using the
following equation [8 10]:
Mc D

3RT
;
E0

(4)

where is the density (in g/cm3 ), T is the temperature (in K), E 0 is the storage
modulus (in MPa), and R is the universal gas constant.
2.9. Infrared spectroscop y
FT-IR measurements were carried out on a Bio-Rad, FTS 175 C spectrophotometer.
The polymers were ground with a planetary ball mill (Pulverisette 7, Fritsch GmbH)
and then sifted to a particle size of less than 24 m. All the polymers and the two
crystalline monomers HEMA/TDI and HEMA/MDI were examined as KBr pellets.
Samples of the resinous monomers were prepared as lms on KBr pellets.
The conversion of methacrylate double bonds was determined using the relative band ratio method [11]. The IR spectra were processed by the Fourier selfdeconvolutio n application, using constant values: y D 1 and x D 0:18 [12].
The fraction of unreacted double bonds was determined by examining the absorption peaks in the range of 1635 1595 cm1 . The methacrylate C C double
bond absorbs at 1643 1635 cm1 .ICDC /, whereas the aromatic one absorbs at
1604 1595 cm1 .IAr/. The aromatic bands remain unchanged during polymerization, whereas the absorption of methacrylate ones decreases as the polymerization
proceeds [13].
The fraction of reacted double bonds was thus calculated using the following
equation:

D 1

ICDC
IAr

pol:

ICDC
IAr

mon:

(5)

3. RESULTS AND DISCUSSION

3.1. Associated monomer molecules

We have previously suggested that the formation of hydrogen bonds involvin g
urethane linkages between pendant groups and cross-links may be responsible for
the apparently underestimated Mc values in the polymers investigate d [1].

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Investigations on the structure of poly(dimethacrylate)s

Table 1.
Association constants (Kass ) and NH chemical shifts (1ass ) of the associated
molecules for urethane dimethacrylate monomers
TDI

HEMA
DEGMMA
TEGMMA
TTEGMMA

MDI

1ass Kass
(ppm) (mol/dm3 )

1ass Kass
(ppm) (mol/dm3 )

1ass Kass
(ppm) (mol/dm3 )

1.34
1.26
1.24
1.81

1.34
1.89
1.89
1.91

0.88
1.19
1.43
1.70

1.66
1.52
1.49
1.10

1.60
1.24
1.03
0.91

0.81
0.62
0.43
0.36

A, B results for different association sites.

We have evaluated the intermolecular interactions on the monomers in solution,

assuming them to be of the same nature as in the corresponding polymers. The
concentration dependence of 1 H-NMR chemical shifts of the NH protons was
employed for this purpose. Quantitative data were processed using the Benesi
Hildebrand equation [7]; the results obtained are listed in Table 1.
Obviously, the values of Kass given in Table 1 are not true association constants
because the system is too complex with respect to the approach employed. However,
if the numerical data are thought to be some measure of the intermolecular interactions, we are allowed to relate them to the structure of the monomers. Thus, the values of Kass decrease with increasing length of the oligoethylen e blocks and we can
conclude that the intermolecular interactions decrease as well. Generally, the association between monomer molecules having aromatic cores, i.e. the OEGMMA/TDI
and OEGMMA/MDI series (Kass D 0:36 1:66 mol/dm 3 , Table 1), is stronger than
for those with linear aliphatic (Kass D 0:27 0:56 mol/dm 3 ) and cycloaliphati c
cores (Kass D 0:32 1:25 mol/dm 3 ) [14]. On this basis, we can expect that in the
corresponding polymers similar structural effects should be observed.
3.2. Direct determination of the network parameter by DMTA
Similarly to what was previously stated for the polymers of aliphatic urethane
dimethacrylates [1], the polymers of aromatic ones, i.e. the OEGMMA/TDI and
OEGMMA/MDI series, exhibit a distinct dependence of the glass transition temperature (Tg ) on the length of the oligoethylene blocks. As can be seen from the
data collected in Table 2, the effect of the central structural unit on Tg is less visible
the Tg values for the series based on TDI and IPDI are quite similar.
The network parameter values calculated based on the DMTA measurements
given in Table 3 are close to MW or smaller; the Mc =MW ratio ranges from 0.56
to 1.06. This could be explained by stronger intermolecular interactions suggested
by the high values of Kass (Table 1). The series based on linear aliphatic cores,
i.e. OEGMMA/HMDI and OEGMMA/TMDI, have low values of Kass [14] and a

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309

Table 2.
Glass transition temperature values measured by DMTA for the
poly(urethane dimethacrylate)s
Tg . C/a
OEGMMA

TDI

MDI

HMDI b

TMDIb

IPDIb

n D 1, HEMA
n D 2, DEGMMA
n D 3, TEGMMA
n D 4, TTEGMMA

192
111
65
33

165
109
75
46

139
67
33
10

148
62
4
20

194
105
83
42

a Measured
b

at a standard frequency of 1 Hz.

Results from previous work [1].

Table 3.
Network parameter values (Mc ) evaluated by DMTA for the poly(urethane
dimethacrylate)s
Polymer of

MW
(g/mol)

Density
(g/cm3 )

T
(K)

E 0a
(MPa)

Mc
(g/mol)

Mc =MW

HEMA/TDI
DEGMMA/TDI
TEGMMA/TDI
TTEGMMA/TDI
HEMA/MDI
DEGMMA/MDI
TEGMMA/MDI
TTEGMMA/MDI

434
523
611
699
511
599
687
775

1.427
1.485
1.452
1.410
1.412
1.535
1.414
1.469

503
433
378
343
478
443
378
353

39
34
23
19
34
51
26
26

459
472
595
635
495
333
513
497

1.06
0.90
0.97
0.91
0.97
0.56
0.75
0.64

a Measured at a standard frequency of 1 Hz at temperature T

within the rubbery

plateau.

Mc =MW ratio in the range of 0.33 3.02 [1]. On the other hand, the series based on
IPDI exhibits intermediate values of Kass [4], whereas the Mc =MW ratios are some
of the smallest (0.38 0.66) [1]. The latter effect is probably due to the presence of
tertiary carbons of aliphatic rings, which may be recognized by DMTA as additional
branch points.
3.3. Conversion of double bonds
According to equation (1), the cross-link density in poly(dimethacrylate) s depends
directly on the conversion of double bonds in the system. For the monomers having
constitutiona l aromatic units, such as the OEGMMA/MDI and OEGMMA/TDI
series, it is possible to determine the conversion of methacrylate double bonds with
the aid of IR spectroscopy, relating the ratio of the absorption of the methacrylate
band to the aromatic one in the spectrum of the polymer to the respective ratio in
the spectrum of the monomer [13].

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Investigations on the structure of poly(dimethacrylate)s

Table 4.
Conversion of double bonds () and the cross-link density (q) in the aromatic
poly(urethane dimethacrylate)s determined using FT-IR spectroscopy

HEMA/TDI
DEGMMA/TDI
TEGMMA/TDI
TTEGMMA/TDI
HEMA/MDI
DEGMMA/MDI
TEGMMA/MDI
TTEGMMA/MDI

0.88
0.96
0.97
0.96
0.75
0.71
0.88
0.93

0.86
0.96
0.97
0.96
0.67
0.59
0.86
0.92

The values of the degree of conversion () and the corresponding cross-link

densities (q) estimated in such a way are listed in Table 4.
Both the conversion and the cross-link density values obtained are rather high,
in most cases approaching maximal ones. In our opinion, these results may be
overestimated, since the DSC measurements yielded considerably lower values of
and q [15]. Nevertheless, the results obtained may form a basis to subsequent
consideration s concerning possible relationships between the cross-link density and
the network parameter in poly(dimethacrylate)s .
3.4. How should we relate Mc to q in poly(dimethacrylate)s ?
The most widely known relationship between the cross-link density and the network
parameter is given by equation (2) [2], which implies that the reciprocal of q, i.e. the
Mc =MW ratio, can be understood as the number-average degree of polymerization
between two branch points (N ), whereas the cross-links are depicted as volumeless
points and do not participate in Mc . In poly(dimethacrylate)s , such an assumption
cannot be valid, since the molecular weight of the monomers forming the crosslinks approach a few hundreds and for high values of q, we should consider the
latter to be an important constituent of the structure of such a network.
Let us consider the cross-link to be included in Mc . If each Mc consists of
N D 1=q repeating units, N 1 of them are those derived from the monomer
molecules with one C C bond reacted, each having a molecular weight equal to
MW . The last unit is derived from the cross-link, i.e. the monomer molecule
with both C C bonds reacted, and may participate in Mc depending on what
functionality of branch points we have assumed.
Assuming a cross-link to form one tetrafunctional branch point (Scheme 2), we
can include half of its weight in a fragment of the chain between two branch points,
i.e. that equal to Mc . Thus, we can express the network parameter as

MW
1
M c.f D4/ D
1 MW C
q
2

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311

Scheme 2.

Scheme 3.

M c.f D4/ D

MW
MW
:

q
2

(6)

However, it seems to be more realistic if we consider the dimethacrylate crosslinks to form two trifunctional branch points between neighbourin g primary chains
(Scheme 3).
The smallest repeating fragment of a network consists of two chains of (N 1)
MW and one of MW . The average Mc is then

2 q1 1 MW C MW
MW
2 1
M c.f D3/ D
D
1 MW C
3
3 q
3
MW
2MW
M c.f D3/ D
:

(7)
3q
3
Both equations (6) and (7) should be considered in boundary conditions with
respect to the conversion and cross-link density. Thus, for complete conversion,
q D 1 and Mc D MW=2 or MW=3, depending on the functionality assumed.
On the other hand, for a small conversion, i.e. approaching 0.5, q is close to
null and thus MW=q is large. Neglecting MW=2 in equation (6) or MW=3 in
equation (7), Mc approaches MW=q, i.e. as in equation (2) for tetrafunctional
branch points assumed, or 2MW=3q for trifunctional ones. In each case, however,
the contributio n of cross-links in Mc results in a reduction in its value with respect to
that resulting from equation (2), especially for high values of the cross-link density.
Thus, the low experimental values of Mc found by DMTA both previously [1] and in
this work for some of the polymers may be explained by the above considerations.
Now, we can compare the values of Mc estimated directly by DMTA with those
calculated based on the conversion from IR and the resulting cross-link density

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Investigations on the structure of poly(dimethacrylate)s

Figure 1. Mc =MW ratios for the series of poly(dimethacrylate)s calculated based on IR spectroscopy
and DMTA.

values in three different modes, i.e. according to equations (2), (6) and (7). The
results, expressed by the Mc =MW ratio, are presented in Fig. 1.
As can be seen from Fig. 1, the Mc values for the MDI series found by DMTA
are much smaller than MW and are rather close to those calculated based on IR
using equation (6), except for the polymer of DEGMMA/MDI for which it is even
smaller than that based on equation (7). For the TDI series, the results based on
DMTA are close to those calculated using equation (2). However, we do not know
to what extent the FT-IR method overestimates the degree of conversion and thus the
resulting cross-link density values. Even if it were a few percent, the speculations
above become incorrect, i.e. the Mc values from DMTA would approach those based
on equation (7) for the MDI series, or those based on equation (6) for the TDI series.
Another factor to be taken into account is how to calculate Mc based on DMTA.
We have been doing this according to Hill [8], i.e. by use of equation (4). The
results reported in the latter work have shown good agreement of the Mc values
measured by DMTA and equilibrium swelling. Another approach was used by
Reiche et al. [16] for poly(dimethacrylate) s of oligoethylene glycols. The networks
were assumed to be of the non-af ne phantom ones and the value of Mc based on

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313

DMTA was multiplied by a factor equal to (f 2/=f , where f is the functionality

of the branch points (the so-called front factor A equal to 1/2 for f D 4 and 1/3 for
f D 3 [17]). If we followed this in the case of the poly(urethane dimethacrylate)s
investigated, the values of Mc found by DMTA would be extremely low, e.g.
Mc =MW D 0:19 for poly(DEGMMA/MDI). For some polymers of the aliphatic
series, it would be even smaller, thus losing reasonable physical meaning.
In summary, we still do not know what is the proper relationship between
the cross-link density and the network parameter in poly(dimethacrylate)s . Most
probably, the networks are extremely non-ideal due to the very high cross-link
density, the presence of a large amount of pendant chains, and, as suggested in
the literature [18], a considerable fraction of entanglements and loops. That is why
they do not comply with such classic relationships as those given by equations (2)
and (4). Non-covalent bonds, such as hydrogen bonds, are additional factors to
be taken into account. Nevertheless, a more in-depth view of the structure of
poly(dimethacrylate) s has been achieved, which was the aim of this work.

4. CONCLUSIONS

Urethane dimethacrylates exhibit intermolecular interactions in solution. When

polymerized in bulk, they form highly cross-linked systems that have characteristic
features of a non-ideal network. In these polymers, the molecular weight of the
cross-links should be considered when relating the network parameter to the crosslink density.

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