Polymer International 43 (1997) 2226

Photopolymerization of Methyl Methacrylate Sensitized by Tris(2,2bipyridine)iron(III)

Aradhana Goswami & Shashi D. Baruah*
Regional Research Laboratory, Jorhat 785 006, Assam, India (Received 1 April 1996 ; revised version received 13 September 1996 ; accepted 10 November 1996)

Abstract : The photopolymerization of methyl methacrylate (MMA) sensitized by tris(2,2@-bipyridine)iron(III) complex, [Fe(bpy) ]3`, was studied at 35C in the 3 presence of an electron donor, triethylamine (TEA) with UV radiation of wavelength 254 nm. The initial rate of polymerization, R , shows a linear dependence p on [MMA] with an exponential value of 118 ^ 004. R varies linearly with the p square root of the photosensitizer concentration up to 200 ] 10~4 mol l~1, and above this concentration, R decreases with the increase of photosensitizer conp centration. The rate of polymerization is not aected by the concentration of the co-initiator, [TEA]. A suitable mechanism for the reaction is proposed to explain the kinetics of the reaction. Key words : tris(2,2@-bipyridine)iron(III) complex, photosensitizer, polymerization, MMA, electron-transfer reaction, redox products. photo-

INTRODUCTION The polymerization of vinyl monomers sensitized by transition metal complexes in the presence of an electron donor compound has been a study of increasing interest. Several of the primary photochemical processes useful in the formation of free radicals capable of initiating vinyl polymerization rely upon initial electron transfer between an excited sensitizer and an added substrate (co-initiator).1 In the case of photoinitiation systems, the desired products are often the initiating free radicals. Iwai et al. have investigated2,3 the photopolymerization of acrylamide (AA) sensitized by various Ru(II) complexes in polar solvents. The Ru(II) complex does not induce the photopolymerization of AA in the presence of an electron acceptor such as methylviologen, but it induces the polymerization in the presence of an electron donor such as triethylamine (TEA). Iwai et al. established that the Ru(II) complexes, which acted as the photosensitizer, could be converted into
* To whom all correspondence should be addressed.

Ru(I) transiently, but were not consumed during the polymerization. Photopolymerization initiated via charge-transfer (CT) interaction involving monomer as one component (photoinduced CT polymerization)4 is well known. Most of the excited metal complexes decompose to form active species, which can initiate the polymerization of vinyl monomers and are consumed during polymerization. However, the literature on photopolymerization systems where the sensitizer does not directly interact with monomer is very scanty.5,6 In such systems, photosensitizers as one of the components of exiplexes were also not consumed during the polymerization.2 The detailed mechanism of photopolymerization in the presence of metal ions is, however, not very clear. The part played by various ligands is also not fully understood. The chemistry of transition metal complexes of chelating nitrogen ligands such as 2,2@-bipyridine (bpy) and 1,10-phenanthroline have been thoroughly studied and their chemical stability, redox chemistry and electron transfer properties are well established.7 Their eects on the polymerization of vinyl monomers are very extensive, and they continue 22

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Photopolymerization of MMA to attract attention in this area. Therefore, we investigated the photopolymerization of vinyl monomers using tris(2,2@-bipyridine)iron(III) complex as a photosensitizer, where the sensitizer could be regenerated by two successive electron transfer reactions.3 The tris(2,2@-bipyridine) complex of iron(III), [Fe(bpy) ]3`, alone did not induce the photo3 polymerization of methyl methacrylate (MMA) under irradiation from UV light, but did in the presence of an electron donor, triethylamine (TEA), which acted as a co-initiator. In this paper, the photopolymerization of MMA sensitized by [Fe(bpy) ]3` is reported in the 3 presence of the co-initiator, TEA. The reactants were irradiated with light of wavelength 254 nm from a low pressure mercury lamp. There is no ground state interaction amongst the three components, i.e. metal complex, TEA and MMA, in a non-aqueous solvent such as dimethylsulphoxide (DMSO). Therefore, the photopolymerization of MMA is carried out by selective excitation of the transition metal complex [Fe(bpy) ]3`, at a constant light intensity. 3 EXPERIMENTAL MMA and DMSO were puried as described in the literature.8 TEA was distilled under reduced pressure before use. 2,2@-Bipyridine (E. Merck) was used without further purication. The complex [Fe(DMSO) ](ClO ) 6 43 was prepared as before.8 Tris(2,2@-bipyridine)iron(III) complex, [Fe(bpy) ]3`, 3 was synthesized from the complex [Fe(DMSO) ](ClO ) and 2,2@-bipyridine (bpy) by the 6 43 method reported in the literature,9,10 The photopolymerization reactions were conducted with an immersion well photochemical reactor (Applied Photophysics). The reactants were irradiated by UV light produced by a low pressure lamp of 16 W which emitted more than 90% of its radiation at 254 nm. The lamp was located in a cooled, double-walled immersion well. Despite the low power (16 W), the UV lamp produced over 3 ] 1018 photons per second (measured by ferrioxalate actinometry in a quartz well), and had a long life and a negligible warm-up time. The photochemical reactor was immersed in a constant-temperature bath at 35C and polymerizations were conducted by irradiating lled tubes at a xed distance. Rates of polymerization (R ) were determined p gravimetrically and dilatometrically as before.8 Dierential scanning calorimetry (DSC), for the determination of the glass transition temperature (T ) of g the polymers, was carried out at a heating rate of 10C min~1 on a Perkin Elmer PC series DSC 7 with 25 mg samples of polymer weighed in aluminium pans. All experiments were carried out in nitrogen atmosphere and the measurement was started as soon as the heat ow in the DSC cell had stabilized.
POLYMER INTERNATIONAL VOL. 43, NO. 1, 1997

23 Intrinsic viscosities were determined in benzene at 25C using a Schott Gerate model AVS 400 automated viscometer. Molecular weights (M ) were computed 1 n from the intrinsic viscosity data by using the relationship :11 [g] \ 869 ] 10~5 M0.76 1 n (1)

RESULTS AND DISCUSSION The initial polymerization rate, R , shows a linear p dependence on [MMA] (Table 1) with a slope of 118 ^ 004. This is in accordance with the general equation for steady-state free radical photoinitiated polymerization. The relationship between R and concentration of p [Fe(bpy) ]3` at constant [MMA] in DMSO is shown 3 in Fig. 1. With low concentration of [Fe(bpy) ]3`, the 3 initial rate of polymerization varies almost linearly with the square root (052 ^ 007) of [Fe(bpy) ]3` concen3 tration (initial portion of Fig. 1), which indicates the square root dependence of R on [Fe(bpy) ]3` concenp 3 tration. For higher concentrations of [Fe(bpy) ]3` 3 ([200 ] 10~4 mol l~1), R decreases with increase of p [Fe(bpy) ]3` concentration. From the slope of the nal 3 portion of the curve, R is inversely proportional to the p square root ([046 ^ 004) of [Fe(bpy) ]3` concentra3

Fig. 1. Plot of R as a function of the square root of p [Fe(bpy) ]3` concentration. [MMA] \ 187 mol l~1 ; 3 [TEA] \ 050 mol l~1 ; irradiation wavelength \ 254 nm ; temperature \ 35C ; solvent \ DMSO.

24

A. Goswami, S. D. Baruah
1 TABLE 1. Data for the relationship between R , molecular weight (M ) and glass n p transition temperature (T ) on concentrations of MMA and [ Fe(bpy) ] 3 for g 3 poly(MMA) prepared photochemically at 35C by the [ Fe(bpy) ] 3TEA system 3 MMA (mol l1) Conc. of Fe(bpy) 3 3 104 (mol l1) 100 100 100 100 100 020 040 060 200 300 445 700 980 Irradiation time (min)

R 105 p (mol l1 s1)

i (dl g1)

1 M

T g (C)

047 075 112 140 187 187 187 187 187 187 187 187 187

180 180 180 180 180 180 180 180 180 180 180 180 180

0573 1102 1719 2213 2601 0522 0645 0912 2700 2400 2100 1560 1300

0159 5 0207 8 0302 0 0318 2 0340 7 0469 0 0419 0 0376 0 0339 7 0275 1

19 700 27 900 45 600 48 900 53 500 81 400 70 300 60 800 53 300 40 700

1224 1245 1268 1320 1326 1328 1319 1288

TEA 050 mol l1 ; irradiation wavelength 254 nm.

tion. This is in agreement with the analytical expression developed by Schultz & Joshi12 for the kinetics of photopolymerization under non-stirring conditions. Hence, it is likely that at high concentration of [Fe(bpy) ]3`, an appreciable participation of primary 3 radical termination takes place and R decreases. A p similar trend at high photoinitiator concentration was also reported by other workers.13h15 Under our experimental conditions, attempts were made to polymerize MMA using [Fe(bpy) ]3` concentrations below 3 500 ] 10~5 mol l~1, but the trace quantity of polymer formed was practically irrecoverable. A few of the rate curves with dierent concentrations of [Fe(bpy) ]3` 3 obtained from dilatometric experiments are shown in Fig. 2. With dierent amounts of triethylamine (TEA) as the co-initiator in the photopolymerization system, R was p found to be independent of [TEA]. This indicates that the presence of TEA in the polymerization medium does not modify the exciter concentration between an excited species and the ground state of the photosensitizer molecules. Therefore, to avoid any possible eect of [TEA] on R , an excess amount of TEA has p been used throughout the course of the study. In the [Fe(bpy) ]3`TEA sensitized photo3 polymerization system, there is no ground state interaction between the metal complex, TEA and MMA in DMSO. The polymerization is carried out by photoexcitation of the metal complex under the inuence of UV radiation of 254 nm. The average rate constant calculated from a rst order plot is found to be 395 ^ 023 ] 10~6 s~1. The molecular weights (M ) of poly(MMA) at various 1 n MMA and [Fe(bpy) ]3` concentrations are also pre3

sented in Table 1. It has been found that M of 1 n poly(MMA) increases with increase of [MMA]. A decrease in M is observed with increase of 1 n [Fe(bpy) ]3` concentration. At higher [Fe(bpy) ]3` 3 3

Fig. 2. Photopolymerization timeconversion plots for MMA in DMSO at 35C initiated by the [Fe(bpy) ]3`TEA system 3 with dierent concentrations of [Fe(bpy) ]3`. Irradiation 3 wavelength \ 254 nm ; [MMA] \ 187 mol l~1 ; [TEA] \ 050 mol l~1. [Fe(bpy) ]3` concentration (in mol l~1) : (a) 3 180 ] 10~3 ; (b) 900 ] 10~4 ; (c) 500 ] 10~4 ; (d) 200 ] 10~4. POLYMER INTERNATIONAL VOL. 43, NO. 1, 1997

Photopolymerization of MMA concentrations an increase in growing chain population takes place, which in turn enhances the polymerization rate and consequently a decrease in the degree of polymerization occurs.16 Primary radical termination will be more likely under these conditions of high photosensitizer concentration. This will also lower the molecular weight of the polymer formed.17 The value of k /k1@2 (where k and k are the rate conp t p t stants for propagation and termination, respectively) was calculated using the well known Mayo expression18 in the form : 1/DP \ (k /k2) ] (R /[MMA]2) ] 1/DP (2) t p p 0 where DP is the number average degree of polymerization and DP is the value of DP in the absence of 0 transfer. Neglecting the chain transfer to MMA, the plot of 1/DP versus R /[MMA]2 at constant concentrations p of TEA and [Fe(bpy) ]3` was linear to a rst approx3 imation (Fig. 3), and from the slope of the plot the value of k /k1@2 was found to be 0071. This value is close to p t the reported literature value18 for a free radical initiator system. This indicates that the [Fe(bpy) ]3`TEA 3 photosensitizer system follows the mechanism of free radical polymerization. In the present system, the average chain length formed under a given set of conditions increases signicantly with time of polymerization, i.e. with increased percentage conversion (Table 2). A similar phenomenon

25
TABLE 2. Data for the decrease in the concentration of monomer (x ) after definite reaction times, intrinsic viscosity and molecular weight for MMA initiated photochemically by the [ Fe(bpy) ] 3TEA 3 system Reaction time (min) 60 120 240 300 360

x (mol l1)

(a /a x )a

i (dl g1)

1 M

009 016 027 030 034

1052 1093 1167 1189 1225

0241 2 0276 0 0281 7 0290 5 0302 4

33 900 40 500 41 600 43 300 45 700

a a is the initial concentration of MMA 187 mol l1. Concentration of Fe(bpy) 3 100 104 mol l1 ; 3 TEA 050 mol l1 ; irradiation wavelength 254 nm.

was also reported for other photopolymerization systems.16 The overall activation energy, E , was found to be a 156 kcal mol~1, which is reasonably close to the reported values for the photopolymerization of MMA.19 The glass transition temperature (T ) of the g poly(MMA) samples at rst increases linearly with increasing monomer concentration and the levels o at about 1326C (Table 1). This indicates that the T of a g given polymer is a function of its chain length.20,21

Kinetic scheme for photopolymerization of MMA sensitized by Fe (bpy ) 3TEA 3

A photosensitizer is regarded as an electron transfer agent, which absorbs light to undergo electron transfer with an electron acceptor or donor and reverts to its original state.2,3 In the [Fe(bpy) ]3`TEA sensitizer 3 system, the photosensitizer, [Fe(bpy) ]3` was rst 3 excited by UV light to form the participating excited state, [Fe(bpy) ]3`*, which undergoes electron transfer 3 with the electron donor TEA. One or more of the resulting redox products should be capable of generating initiating radicals (R~) for polymerization. This may be described as follows : h [Fe(bpy) ]3` [Fe(bpy) ]3`* (3) 3 3 [Fe(bpy) ]3`* ] TEA ([Fe(bpy) ]3` . . . TEA)* 3 3 (exciplex) [Fe(bpy) ]2` ] TEA~` 3 (redox products) (4)
Fig. 3. Plot of 1/DP versus R /[MMA]2 for photop polymerization of MMA at 35C using the [Fe(bpy) ]3`TEA 3 photosensitizer system. Concentration of [Fe(bpy) ]3` \ 100 3 ] 10~4 mol l~1 ; [TEA] \ 050 mol l~1 ; irradiation wavelength \ 254 nm. POLYMER INTERNATIONAL VOL. 43, NO. 1, 1997

redox products R~

(5)

where R~ is the primary free radical formed. Efficient electron transfer requires that the excitation energy of the photosensitizer is sufficient to eect the

26 electron transfer process, including separation of the redox products. Photopolymerization rate is normally expressed as :22 R \ k [M]('I /k )1@2 (6) p p a t (7) \ k [M]('I [1 [ e~e*PI+l@kt])1@2 p 0 where k and k are the rate constants for propagation p t and termination, respectively, I and I are the intens0 a ities of the incident and absorbed light, respectively (in Einstein l~1 s~1), PI is the species which undergoes photoexcitation, e is the molar extinction coefficient of PI at the irradiation wavelength (254 nm), l is the thickness of the reaction system and ' is the quantum yield for initiation. For small absorbances (e[PI]l > 1), eqn (7) becomes : R \ (k /k1@2)[M] ] (23'I e[PI]l)1@2 (8) p p t 0 In fact, by keeping [PI] 10~5 mol l~1, I did not a vary appreciably with the distance of the reaction vessel from the light source, and under these conditions the initial rate of polymerization varied linearly with the square root of [PI]. For higher concentrations of PI ([10~4 mol l~1), I \ I (1 [ 10~e*PI+l) B I and the initial R must be a 0 0 p independent of [PI]. In the unstirred polymerization system, a decrease of the initial polymerization rate with increased [PI] was observed at high absorbance values.23 This is in agreement with the following expression developed by Schultz & Joshi12 for kinetics of photoinitiated polymerization under non-stirring conditions : R \ (k /k1@2) ] (M('I )1@2[M]N/Me[PI]lN)1@2 p p t 0 ] (1 [ 10~e*PI+l@2)

A. Goswami, S. D. Baruah [Fe(bpy) ]3` may be converted into [Fe(bpy) ]2`. 3 3 From our study, it appears that the present photosensitizer system is a very efficient one for producing faster photopolymerization than conventional photosensitizers.

ACKNOWLEDGEMENTS The authors wish to thank the Director, RRL-Jorhat, for permission to publish the results. We thank Professor N. N. Dass of Dibrugarh University for his encouragement and suggestions during the course of the work.

REFERENCES
1 Eaton, D. F., Pure Appl. Chem., 56 (1984) 1191. 2 Iwai, K., Uesugi, M. & Takemura, F., Polym. J., 17 (1985) 1005. 3 Iwai, K., Uesugi, M., Sekabe, T., Hazama C. & Takemura, F., Polym. J., 23 (1991) 757. 4 Shirota, Y. & Mikawa, H., J. Macromol. Sci., Rev. Macromol. Chem., C16 (197778) 129. 5 Tazuke, S. & Kitamura, N., J. Chem. Soc., Chem. Commun., (1977) 515. 6 Asanuma, T., Gotoh, T., Tsuchida, A., Yamamoto, M. & Nishijima, Y., J. Chem. Soc., Chem. Commun., (1977) 485. 7 Potts, K. T., Bull. Soc. Chim. Belg., 99 (1990) 741. 8 Baruah, S. D., Goswami, A. & Dass, N. N., Polym. J., 24 (1992) 719. 9 Hussain, S. & Dass, N. N., Ind. J. Chem., 19A (1980) 189. 10 Baruah, S. D. & Goswami, A., J. Appl. Polym. Sci., (in press). 11 Fox, T. G., Kisinger, J. B., Mason, H. F. & Schuele, G. M., Polymer, 3 (1962) 71. 12 Schultz, A. R. & Joshi, M. G., J. Polym. Sci., Polym. Phys. Edn, 22 (1984) 1753. 13 Abbas, A. & Tajuddin, I., J. Photochem., 35 (1986) 87. 14 Aslam, M., Anwaruddin, K. & Natarajan, L. V., Polym. Photochem., 5 (1984) 41. 15 Goswami, A., Baruah, S. D. & Dass, N. N., Polym. Bull., 35 (1995) 561. 16 Ghosh, P. & Jana, S., J. Macromol. Sci.,-Chem., A17 (1982) 743. 17 McGinnis, V. D., Provder, T., Kuo, C. & Gallopo, A., Macromolecules, 11 (1978) 393. 18 Billingham, N. C., in Comprehensive Polymer Science, eds G. Allen & J. C. Bevington. Pergamon, Oxford, 1989, vol. 3, Ch. 4. 19 Ghosh, P. & Mitra, P. S., J. Polym. Sci., Polym. Chem. Edn, 13 (1975) 921. 20 Fox, T. G. & Flory, P. J., J. Appl. Phys., 21 (1950) 581. 21 Vansco Smzercsanyi, I., White, B. & Vanco, G. J. J., J. Appl. Polym. Sci., Appl. Polym. Symp., 51 (1992) 241. 22 Odian, G., Principles of Polymerization, 2nd edn. Wiley Interscience, New York, 1981, p. 209. 23 Mateo, J. L., Bosch, P., Catalina, F. & Sastre, R., J. Polym. Sci., Part A : Polym. Chem., 28 (1990) 1445.

(9)

Equation (9) shows that R is inversely proportional p to the square root of [PI] at higher concentrations.

CONCLUSIONS The experimental results with the [Fe(bpy) ]3`TEA 3 photosensitizer system are in accordance with the general expression for steady-state free radical photopolymerization. The conversion depends on polymerization time and photosensitizer concentration at constant light intensity. There is practically no eect of co-initiator concentration. In the photopolymerization,

POLYMER INTERNATIONAL VOL. 43, NO. 1, 1997