Volume 96A, number 2

PHYSICS LETTERS

13 June 1983

COLOURATION OF RHODAMINE B IN PMMA BY AQUEOUS HCI SOLUTION

AND IN THE COPOLYMER OF METHYL METHACRYLATE WITH METHACRYLIC ACID
Jun'ichiro MUTO and Fumito HIGUCHI
Department of Instrumentation Engineering, Faculty of Engineering, Keio University,
3-14-1 Hiyoshi, Kohoku, Yokohama 223, Japan
Received 1 July 1982

A rhodamine B doped PMMAsample is made by the solution polymerization method. It is found that the reddish
colottr of rhodamine B molecules reduces greatly during polymerization and that the once reduced colour of rhodamine
B recovers by immersion of the sample in aqueous HCI solution. Discolouration of rhodamine B is diminished in the
copolymer of methyl methacrylate with methacrylie acid.

The use of a solid matrix for dye lasers obviates

many of the problems associated with static or flowing
solution dye systems, e.g., convective schlieren, evaporation, flow fluctuation, solvent or dye poisoning,
system ruggedness and maintenance. Polymethyl
methacrylate (PMMA) is a highly transparent plastic
and is used as a solid dye laser matrix and optical fibre.
Rhodamine B(RhB) and rhodamine 6G(Rh6G), most
well-known laser dyestuffs, have both been succeeded
to lase in PMMA [ 1].
Methods of producing dye impregnated plastics
may be characterized as either bulk or solution polymerization methods whereby laser dyes are added to
a solution of catalysts and monomers before polymerization, or at some point in time before the final polymerization of the monomers into the solid matrix.
The dye may also be doped in the plastic by a concentration-difference diffusion method in which a plastic
matrix is immersed in a solution of dissolved organic
lasing dye and a solvent at a suitable dye concentration,
pH and temperature.
The polarity of RhB is reduced by the coordination
of methacrylic acid(MA), oleic acid or stearic acid, and
then the solubility of RhB in methyl methacrylate (MMA)
is increased by the addition of these acids. Actually
it became possible to dope RhB in the copolymer of
MMA with MA at sufficient concentration for lasing
performance [2]. A decrease in photo and thermal
0 031-9163/83/0000-0000]$ 03.00 1983 North-Holland

bleaching of Rh6G was realized in P(MMA + MA) [3].

Corresponding photo and thermal deterdation results
of RhB in P(MMA + MA) have not yet been obtained.
In view of the above situations, we have fabricated
a RhB doped PMMA sample by the solution polymeriza.
tion method and find that the reddish colour of RhB
molecules decreases greatly during the polymerization
process and that the once reduced colour of RhB/PMMA
recovers by immersion of the sample in aqueous hydrochloric acid solution. RhB is observed to be less
discoloured in P(MMA + MA).
RhB(Eastman Kodak, laser grade) was dissolved in
vacuum distilled MMA solution. Polymerization catalyst was azobisisobutyronytrile(AIBN). 1 mg of AIBN
was used for 1 ml solution. To obtain a RhB doped
P(MMA + MA) sample, vacuum distilled MA was added to the solution. The solution was bubbled with nitrogen gas and kept in a glass container. Polymerization
was performed in a water bath at 40C for 4 days. The
samples obtained were cut and finally polished with 0.3
m alumina.
The samples were 30 mm in diameter and 5 mm
thick. The RhB concentration of the sample is typicall y 7 X 10 -5 M.
Absorption spectra of RhB/PMMA immersed in
7.2 M aqueous HC1 solution at 40C for different immersion times are shown in fig. 1. Absorption coefficients of the sample are found to increase with in101

Volume 96A, number 2

PHYSICS LETTERS

1
HCt

7214

~E

1c]

1:

740 h

2:

265h

3:

~,3h

4:

g,

g_ 5
2,
o

0 ~,

-r

400

--

450

500
Wavelength

550

600

( nrn )

Fig. 1. Absorption spectra of RhB soaked in 7.2 M aqueous

HCI solution at 40C for different immersion times between
0 and 74.0 h.
creasing immersion time in the measured wavelength
region between 600 and 400 nm. Similar spectral behaviour is seen for different immersion temperatures
between 5 and 56C and HC1 concentrations between
0 and 7.2 M. It may be remarked that the maximum
molar absorption coefficient of RhB in ethanol is
about 2.5 X 105 M-1 cm -1, whereas the corresponding
value in PMMA, as seen in fig. 1, is very low, i.e. 0.3
104 M-1 cm -1 . RhB is exposed to HC1 vapour at
room temperature, colouration of the sample is clearly
recognized.
Rhodamine dyes that carry the COOH group become colourless lactonic state in non-polar solvents,
because the n-electron system of the dye chromophore
is interrupted (see fig. 2). Actually, lactonic RhB is
formed in benzoic solution in a reversible reaction [4].
In polar solvents, such as alcohol and water, the lactonic RhB has a tendency to open the closed ring
with a resulting separation of charges, forming a coloured zwitterion.

(C 2 H 5 ) 2 N , ~ O , , ~ . ~ I ( C 2 1 . . 1 5 ) 2

[~
[A]

13 June 1983

Our PMMA sample is in an amorphous state and

shows atactic form, and owing to steric hindrances,
the polymer chain cannot take all configurations allowed by free rotation about the chain molecules. It
is observed that the dipole moment of the long-chain
PMMA molecule per monomer unit is smaller than that
of MMA [5]. Presumably, the polarity of PMMA
molecules surrounding RhB is lessened as polymerization proceeds and then the dye molecules become
colourless lactone. The Rh6G/PMMA sample, made
by the solution polymerization method, is observed
to reduce its colour scarcely during polymerization,
which is reasonable since Rh6G has esterified the
COOH group and the formation of a lactonic state is
prevented. By the introduction of aqueous HC1 solution into PMMA, water molecules form H-bonds
between HC1 and the segments of the polymeric
material and causes the loosening of PMMA material

[6].
Fig. 3. shows a change in peak molar absorption
coefficient of RhB/PMMA, Act, as a function of the
immersion time between 5 and 56C and at a HC1 concentration of 7.2 M. Here Act = (peak molar absorption coefficient of the sample before immersion)
- (that after t hours immersion). In fig. 3, Act seems
to increase as the square root of the immersion time.
In fig. 4, Act versus immersion time of RhB/PMMA
soaked in 7.2 M solution at temperatures between 5 and
56C is presented, in which Act increases approximately
as the square root of the immersion time at smaller immersion times and decreases, at larger immersion times.
Similar behaviours are seen for RhB/PMMA soaked in
the solution of HCI concentration below 7.2 M.
Taking into consideration the reversible reaction
of lactonic RhB in fig. 2, and also the non-polar nature
of PMMA mentioned above in addition to the chemically active behaviour of the hydrogen ion, we may sup-

CI-

f
%/',,c//-,,f
COOH

COOH

l..~. 0

[BJ

Fig. 2. Structural formulae of RhB. [A] shows salt form and [B], formation of lactonic RhB in a reversible way.
102

Volume 96A, number 2

PHYSICS LETTERS

the sample is observed for RhB/PMMA soaked in pure

aqueous solution (see fig. 4). Perhaps,water has also
some activity, small as it is, to open the lactonic ring
of the RhB molecule.
When diffusion of a solvent occurs in a polymer
slab under isothermal conditions, and the slab contains
a uniform initial distribution of a solvent, Fick's law
of diffusion for small diffusion times becomes [8]

xl~ 4

56 ,.C~
//i;30C

Immersion Ti

}1/2

(1)

Wt/W.o = 2 (Dtprd2) 1/2 ,

13 June 1983

(hI/2)

Fig. 3. Change in peak molar absorption coefficient of RhB/

PMMA, AS, versus immersion time at different solution temperatures between 5 and 56C. HC1 concentration: 7.2 M.

pose that by immersion of the RhB/PMMA sample in

aqueous HCI solution, the H + ion diffuses into the
sample and effectively works to open the closed ring
of lactonic RhB resulting in the recovery of the RhB
colour in the sample.
It is said that water in PMMA acts as a plasticizer
for the cooperative motion of the polymer backbone
and appears to exist as isolated molecules or small
clusters [7]. A slight increase in the absorption of

where Wt denotes the total amount of diffusing substance which has entered into the sheet at time t; W=,
the corresponding quantity after infinite time; d, onehalf of the slab thickness, and D is the diffusion coefficient.
Our results in figs. 3 and 4, that Act is proportional
to the square root of the immersion time at small immersion times, may be reasonable provided that the
H ion enters into the sample followed by Fick's law
of diffusion and that Aa increases linearly with the
amount of diffusion substance, i.e. H ion in the solution. The decrease of Act in fig. 4 at larger immersion
times may be due to the destruction of RhB by HC1.
Further detailed studies concerning the diffusion of

~10~

10

10~

u.

c
o
k~
o.

1[

2:

2.4 M

~
o

(Immersion Timel/e

10
(h1/~1

Fig. 4. Change in peak molar absorption coefficient of RhB/

PMMA, AS, versus immersion time at HC1 concentration
between 0 and 7.2 M. Solution temperature: 40C.

~
MA Concentrotion

'

10
(% )

15

Fig. 5. Maximum molar absorption coefficient of RhB/P(MMA

+ MA) versus MA concentration.

103

Volume 96A, number 2

PHYSICS LETTERS

H 2 0 - H C 1 into PMMA will be needed to understand

fully the colouration o f the sample.
Now, we examine the absorption behaviour of
RhB in P(MMA + MA). Discolouration o f RhB in
P(MMA + MA) tends to become less with increasing
MA concentration (see fig. 5). In our experiments,
RhB concentration is below the maximum solubility
in MMA solution, and the addition of MA to MMA
does not seem to improve the solubility of RhB
molecules in the solution. MA is different from MMA
in that one of the COOCH 3 groups is replaced b y
COOH, i.e., non-esterified carboxyl group. The H
ion in the' COOH group of MA is thought to be effective to open the mentioned colourless lactonic RhB
in the polymer matrix.
Hydrolysis of PMMA in sulphuric acid gave a polymer containing 36% MA [9]. Colouration of RhB/
PMMA is expected when the sample is immersed in
H2SO 4 solution. Unfortunately, RhB in PMMA is
found destroyed by the diffusion of H2SO 4 into the
RhB/PMMA sample.

104

13 June 1983

The authors wish to thank Mr.S. Iwata for his assistance in the present work.

References
[1 ] O.G. Peterson and B.B. Snavely, Appl. Phys. Lett. 12
(1968) 232.
[2] K. It0h, H. Kusakawa and T. Takahashi, Oyo Butsuri 39
(1970) 1067 (in Japanese).
[3] F. Higuchi and J. Muto, Phys. Lett. 81A (1981) 95; 86A
(1981) 51.
[4] R.W. Ramette and E.B. Sandel, J. Am. Chem. Soc. 78
(1956) 4872.
[5 ] W.R. Wringham and J.V. Pawkins, Polymer handbook,
Vol. 4, eds. J. Braundrup and E.H. Immergut (Interscience, New York, 1967) p. 331.
[6] V.N. Kestl'man, I.A. Kershunov, N.F. Novotorov, R.A.
Lazareva and L.N. Magazinova, Sint. Fiz. Khim. Polim.
11 (1973)57 [Chem. Abstr. 80 (1974) 3938z].
[7] A.S, Gilbert, R.A. Pethric and D.W. Phillips, J. Appl.
Polym. Sci. 21 (1977) 319.
[8] J. Crank, The mathematics of diffusion (Oxford Univ.
Press, London, 1967) ch. 4.
[9] A.E. Kurikova and D.A. Aranovich, Tr. Khim. Khim.
Tekhnol. 1 (1973) 102 [Chem. Abstr. 80 (1974)
83852e].