Eur. Polvrn. J. Vol. 23, No. 2, pp. 105 108, 1987 0014-3057/87 $3.00+0.

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Printed in Great Britain Pergamon Journals Ltd

A STUDY OF THE POLYMERIZATION OF

ACRYLATES USING ELECTRON BEAM
RADIATION
R. S. DAVIDSON, R. J. ELLIS and S. A. WILKINSON
Department of Chemistry, The City University, Northampton Square, London ECIV 0HB, U.K.
and
C. A. SUMMERSGILL
Wiggins Teape Research and Development Ltd, Butlers Court, Beaconsfield HP9 IRT, U.K.

(Received 12 June 1986)

Abstract--The formation of surface coatings by three difunctional acrylates and one trifunctional acrylate
by polymerization induced by electron beam radiation is described. Physical testing (solvent resistance and
pencil hardness test) indicates that the properties of the coatings change as they are exposed to increasing
amounts of radiation. Fourier Transform Infra Red-Photoacoustic Spectroscopy was used to measure the
extent of double bond consumption under irradiation; it was found that reactive double bonds were
consumed at relatively low doses (< 10 kGy) indicating that film properties are extensively affected by
radiation induced reactions in the polyacrylate. A new reactive diluent, dibutyltin diacrylate, was shown
to cure extremely rapidly to give hard coatings.

INTRODUCTION radiation is continued. Clearly it would be useful to

The production of surface coatings by the poly-
merization of low molecular weight materials under
the influence of u.v. light and electron beam radiation
is a growing industry. The process of polymerization
is highly dependent upon the method of irradiation
employed. Thus depth of cure attainable by u.v.
curing is determined by the absorption characteristics
of the initiator, the absorption properties of the
oligomer/diluent, the retarding effect upon poly-
merization at the surface by oxygen and, if the film
is pigmented, the optical properties (e.g. refractive
index) of the pigment including its absorption
properties [1]. A film cured under u.v. radiation may
therefore show a lack of cure at the surface (due to
oxygen inhibition), full cure part of the way through
the film and little cure at the bottom of the film due
to lack of penetration of the exciting light to these
depths. By way of contrast, electron beam radiation
generates radicals in a random manner throughout
the film and as a consequence the extent of cure is
uniform [2]. Since the space between the film and the
window of the apparatus housing the electron gun is
flushed with nitrogen or other inert gases, little
inhibition of surface cure is observed. The term cure
is widely used and, in the case of u.v. initiated
polymerization of unsaturated compounds, this can
be related to the number of double bonds consumed.
In the case of electron beam radiation of such
materials, the polymerization via the consumption of
double bonds is attended by interaction of the radi-
ation with the oligomer and the newly formed poly-
mer, leading to chain scission and crosslinking [3]. A
rather crude picture of the electron beam induced
curing process is that the unsaturated linkages par-
ticipate in the early stages to give a surface coating,
the latter then undergoes further changes as the
105
separate those properties which develop as a result of
olefin polymerization and those which ensue.
There are several spectral methods available for
determining the number of double bonds consumed
in the polymerization of unsaturated materials such
as acrylate ester, u.v. Absorption[4] and i.r.
spectroscopy [5] appear to be the favourites but there
is growing use of magic angle spinning ~3C-NMR [6].
When surface coatings are being studied, the success-
ful use of these techniques usually requires the poly-
mer film to be separated from the substrate. Often
this is not possible. To examine the intact
film-substrate laminate, one has to resort to such
techniques as multiple internal reflectance spec-
troscopy or diffuse reflectance. The former method is
impractical other than for qualitative use since, owing
to the difficulty of achieving uniform contact between
the sample and the thallium bromide crystal, it is
impossible to get consistent results. Diffuse
reflectance spectroscopy has great potential now that
spectrometers having signal averaging facilities are
available. However, this technique is unsuitable for
use with glossy coatings such as those produced by
the polymerization of acrylates [7]. A new technique
of some promise is Fourier Transform Infra Red
Photoacoustic Spectroscopy (FTIR-PAS) [8]. A pre-
liminary report by Royce et al. [9] has shown that this
technique can be used to examine the extent of
oxygen inhibition which occurs in the u.v. induced
curing of acrylates. The technique is not restricted to
the examination of surfaces since, by varying the
velocity of mirror in the interferometer, depth
profiling can be achieved.
We now report upon the use of FTIR-PAS to
measure the degree of cure in acrylate films poly-
merized using electron beam irradiation.
106 R.S. DAVIDSONet al.

EXPERIMENTAL Table 2. Physical test results for DBTDA

The acrylates tested included 1,6-hexanediol diacrylate
(HDDA) (Cray Valley Products Ltd), trimethylolpropane
triacrylate (TMPTA) (Cray Valley Products Ltd), tri-
propyleneglycerol diacrylate (TPGDA) (Cray Valley Prod-
ucts Ltd) and di-n-butyltin diacrylate (DBTDA) [10]. These
materials were coated onto Gateway Natural Tracing paper
(supplied by Wiggins Teape Ltd). This was chosen for its
purity, smoothness and holdout properties. Film thicknesses
employed were in the region of 1(~30 microns.
Coatweights were determined by the average weight
difference between coated and uncoated samples of the same
dimensions.
Electron beam radiation was carried out using an Otto
Durr electron beam unit model No. E.S.H. 150/130. The
radiation dose was determined by varying the current
applied to the cathode for the given voltage used.
FTIR-PAS spectra were recorded by cutting out a sample
of the coated paper and inserting it into a Princeton PAS
cell Model No. 6005. Spectra were recorded on a Nicolet
60-SX FTIR spectrometer using a mirror velocity of
0.122 cm sec ~. Five hundred scans were collected before the
data were treated. The spectrum obtained in this way was
ratioed against a spectrum of carbon black.
Solvent rub tests were carried out on cured films as
follows. A felt pad soaked in acetone was mechanically
rubbed back and forth across the surface of the sample
under test held flat under tension on a S.A.T.R.A. rub tester
and the pencil hardness of films was assessed by drawing a
sample strip under the lead using a pencil with changeable
0.5 mm flattened leads. This method is based on the ASTM
(D3363) 27.
RESULTS AND D I S C U S S I O N
The reactive diluents H D D A , T P G D A and
T M P T A were coated onto paper and exposed to
known doses of irradiation. H D D A and T P G D A
gave satisfactory coatings which were tested for sol-
vent resistance (solvent rub test) and pencil hardness
(Table 1). Unfortunately, films obtained using
T M P T A showed areas of pitting, making them un-
suitable for testing by mechanical means. These
rather empirical tests (the results at best are only
qualitative and are very much operator dependent)
show that, as the radiation dose is increased, cross-
linking is increased. Using these methods, a com-
parison was made of the film forming properties by
T P G D A and D B T D A . The results for D B T D A are
shown in Table 2. The D B T D A proved to be a
Radiation Coatweight Solvent Pencil
dose/kGy g 2 rub hardness
2.5 21.4 226 2H
5 28.4 261 2H
10 25.5 >500 2H
20 29.2 > 500 > 3H
40 29.6 > 500 > 3H
60 26.3 >500 >3H
remarkable material in that it yielded tack-free coat-
ings with doses in the range (1-2.5 kGy). F r o m Table
2, it can be seen that hard films are obtained at low
doses with evidence for extensive crosslinking.
The data presented in Tables 1 and 2 give no
indication as to when all the double bonds have been
consumed in the polymerization. In some earlier
work [9], a comparison was made between the extent
to which double bonds are consumed upon the u.v.
initiated curing of monofunctional, difunctional and
trifunctional acrylates. It was found that the number
of remaining double bonds increased as the acrylate
functionality was increased from one to three.
The films used to obtain the results shown in
Tables 1 and 2 were examined by F T I R - P A S . That
excellent spectra can be obtained by this oft maligned
technique can be seen from Fig. ! which shows a
typical spectrum from a cured acrylate film. The
presence of the carbonyl group ( ~ 1 7 3 0 c m I) and
residual double bonds ( ~ 1 6 4 8 and 809 cm ~) is
clearly visible although resolution of the saturated
and unsaturated ester carbonyl groups is poor. Spec-
tra were recorded for all the samples. In each case the
coating was sufficiently thick as to prevent spectral
information from the paper substrate interfering with
the acrylate spectra. An indication as to the number
of double bonds remaining in films exposed to the
radiation is given by the intensity of the peak at
810 cm ~ (out of plane C - H bending). However, the
intensity of any peak in an F T I R - P A S spectrum is
determined by both optical and thermal properties of
the film [8].
The depth penetrated by radiation of a particular
frequency is given by:
Depth of penetration ({fl)=~ where fl = EC
C = concentration of absorbing chromophore.

Table 1. Physical test results for H D D A E = extinction coefficient of chromophore at the

Radiation Coatweight Solvent Pencil frequency of the radiation.
dose/kGy g- 2 rub hardness
2.5 17.4 32.5 H The thermal diffusion depth, Ps \pC~oJ
5 18.8 55 H
l0 11.1 75 2H
where
20 10 500 2H
40 10 > 500 2H = thermal conductivity of the film.
60 19.4 >500 >3H
p = density of the film.
Physical test results for T P G D A o~ = modulation frequency of the light source
Radiation Coatweight Solvent Pencil (which is related to the mirror velocity in the
dose/kGy g 2 rub hardness interferometer).
2.5 31.3 36 HB
5 30.7 74 2H The intensity o f a PA signal is dependent upon d e and
10 22.3 53 2H #s. For the films cured by radiation, we go from a
20 19.3 191 2H thick viscous film to a coating the hardness of which
40 16.4 161 3H
increases as the radiation dose increases. F r o m these
60 31.4 >500 >3H
facts, it is clear that the thermal properties of the
 Polymerization of acrylates 107
o
e~ o
o
0 0
r~
=°8
,~- b-
g Q
o ai
ko tl)

~t
m
o
o3

/
I I I I J
1950 1750 1550 1350 1150 950 750

Wavenurnbers

Fig. 1

surface film change as the radiation dose increases of the double bonds that are to be utilized have been
and consequently the intensity of the spectrum will consumed by 10 kGy radiation. This is a clear indi-
reflect these changes in properties as well as the cation that, following the polymerization of the acryl-
concentration of the chromophores. To overcome ate groups, there is further modification (in particular
these problems it is necessary to ratio the size of the crosslinking) to the films as a result of their being
peak under investigation against an absorption band exposed to radiation.
which changes little in intensity throughout the cu-
ring process. For this purpose, we selected the peak lo
due to the carbonyl groups at 1740 cm ~. The lack of
+ TMPTA
resolution between the unsaturated and saturated o8 (810/1740 cm 1)
carbonyl groups lead to the little changes in shape of
o HDDA
this peak during irradiation. The results are sum- (810/1540 crg
marized in Fig. 2. Features worthy of note are that 08
there is a far greater n u m b e r of residual double bonds • TPGDA

in the cured coating of the trifunctional acrylate or (810/1740 cm :)

( T M P T A ) compared with the difunctional acrylates,

X DBTDA
some double bonds in the diacrylate do not par- -~ 06 (810/1730 cm 1)
ticipate in polymerization and D B T D A polymerizes
far more rapidly than the other difunctional acryl-
ates. The n u m b e r of double bonds utilized in the ~ 05
polymerization is related to the rate at which the
formation of a gel occurs. Once a highly viscous ~" 04
semi-rigid structure is produced, the only double
bonds which can participate in reaction are those
0.3
which are located next to a radical or latent radical
centre. Since triacrylates crosslink to a greater extent
than diacrylates, gelation will occur more quickly 02
with the compounds leading to a greater number of
residual double bonds, ol ~ . --_...====
When the results in Fig. 2 are compared with those x ~ ~ x ~ X ' - -

in Tables 1 and 2, it is interesting to see that the i I I I

properties tested by the solvent resistance and pencil o 25 5 10 ~5 20
Radiation dose/kGy
hardness test continue to change as the radiation dose
increases, despite the fact that (from the figure), most Fig. 2
108 R.S. DAVIDSONet al.
The results showed the utility of F T I R - P A S for
quantifying the degree of cure and establish, what has
been suspected for a long time, that electron beam 2.
curing of reactive diluents and oligomers containing
acrylate groups involves far more than consumption 3.
of the unsaturated groupings.
4.
Acknowledgements--The City University gratefully ac- 5.
knowledges the financial support given by Wiggins Teape
Research and Development Ltd. In addition the project 6.
would not have been possible without the technical expertise
and stimulating support given by Messrs R. E. Wallis and 7.
M. R. Chamberlain (both of Wiggins Teape). We also thank
Nicolet Instruments and Polaron for allowing us to use their 8.
FTIR spectrometers.
9.
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Y. Tabata. Proc. Radcure Conf. May 1985, Basle,
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A. Charlesby. In Polymer Science (Edited by A. D.
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G. Plews and R. Phillips. J. Coat. Technol. 51 (648), 66
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V. P. Thalacker and T. F. Boettcher. Proc. Radcure
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A. Rosencwaig. Photoacoustics and Photoacoustic Spec-
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R. D. Small, J. A. Ors and B. S. H. Royce. In Polymers
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