European Polymer Journal 38 (2002) 885893 www.elsevier.

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A study on the reaction between N-substituted p-phenylenediamines and ozone: experimental results and theoretical aspects in relation to their antiozonant activity
Franco Cataldo *
Soc. Lupi Chemical Research Institute, Via Casilina 1626/A, 00133 Rome, Italy Received 8 June 2001; received in revised form 5 September 2001; accepted 6 September 2001

Abstract The following p-phenylenediamines (PPD): N ,N,N 0 ,N 0 -tetramethyl-p-phenylenediamine (TMPPD), N,N 0 -dimethylbutyl-p-phenylenediamine (6PPD), N,N 0 -diaryl-p-phenylenediamine (DPPD), tris-(N -dimethylpentyl-p-phenylenediamine)-N 0 ,N 0 ,N 0 -1,3,5-triazine (6PPDTZ), have been oxidized under the action of O3 in diluted solutions. In all cases the radical cation or semiquinone radical was the rst derivative formed by monoelectronic oxidation of the substrate. The radical cation has been studied by electronic spectroscopy and the electronic spectral changes of all mentioned PPD has been followed as function of the ozonation time. The results have been discussed in the frame of the antiozonant properties of these PPD which are used as antiozonant agents in diene rubber protection. It is shown that the antiozonant activity of each PPD considered correlates with the free enthalpy of formation of the respective radical cation. The lowest is the free energy of formation of a PPD radical cation and the highest is the antiozonant activity in a diene rubber compound. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Ozone; p-Phenylenediamine (PPD); Radical cation; Semiquinone radical electronic spectroscopy; Antiozonant; Diene rubber; Protection

1. Introduction N ,N -substituted p-phenylenediamines (PPD) are the most widely used antidegradant and antiozonants agents for diene rubber [1,2]. Although other classes of antiozonants are well known [2], and some of them nd some special application mainly in niche sectors, the PPDs are by far the most eective and widely used agents. The general reaction mechanism of ozone with aliphatic and aromatic amines has already been proposed and reviewed by Bailey [3] and by Rakovsky and Zaikov [2]. In the present paper we would like to report our experimental results obtained by electronic spectroscopy concerning the ozonation of some commercially avail-

able PPD and of N ,N ,N 0 ,N 0 -tetramethyl-p-phenylenediamine (TMPPD). The interpretation of the experimental results has led us to clarify the early stage of reaction of PPD with O3 which involve the formation of PPD radical cation followed by the formation of the quinonediimine (QDI) derivative. Once claried this mechanism, we show that by theoretical calculations it is possible to predict the reactivity with O3 of any substituted PPD on the basis of the free enthalpy of formation of the radical cation of each PPD molecule.

2. Experimental 2.1. Materials and experimental procedure

Tel.: +39-06-205-5084; fax: +39-06-205-0800. E-mail address: cdcata@ashnet.it (F. Cataldo).

In the present study, ozone has been generated electrochemically [4], as in all our previous studies [510]

0014-3057/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 0 1 4 - 3 0 5 7 ( 0 1 ) 0 0 2 4 8 - 8

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and the PPD used were commercial grades N ,N 0 -dimethylbutyl-p-phenylenediamine (6PPD), N ,N 0 -diarylp-phenylenediamine (DPPD), tris-(N-dimethylpentylp-phenylenediamine)-N 0 ,N 0 ,N 0 -1,3,5-triazine (6PPDTZ). The latter PPD is a relatively new and non-staining antiozonant commercialized under the trade name of Durazone by Uniroyal Chemicals. Only TMPPD di-hydrochloride has been purchased from Aldrich. The ozonation reactions were conducted in analytical grade CHCl3 from Fluka or in distilled water solution by bubbling the ozonized oxygen into the PPD solutions. The average ozone content by weight over oxygen was about 10% and was determined iodometrically [4]. Ozone was produced at a rate of 3:43 107 mol/min in all cases. The solution volume used in each ozonation study was 25 or 50 ml as specied case by case in the text. After opportune intervals of ozonation times the electronic spectra have been recorded on a Shimadzu UV160A spectrophotometer.

2.2. Theoretical calculations The theoretical calculations concerning the free enthalpy of formation of the molecules considered in this work have been conducted by using AM1 method. Also the free enthalpy of formation of the radical cation of each molecule has been calculated with the same method, by extracting one electron from one nitrogen atom.

3. Results and discussion In our previous works [7,8] which we have reviewed recently [11,12], we have shown that long unsubstituted and substituted polyene chains generate radical cations

Fig. 1. Electronic spectra of TMPPD. (A) Pure TMPPD2HCl 1:77 104 M in H2 O. (B) Same as in A after 5 s ( ) and after 300 s () ozonation. (C) TMPPD2HCl 5:65 104 M in H2 O from bottom to top respectively after 25, 65 and 120 s ozonation. (D) TMPPD 4:22 105 M in CHCl3 : the curve with the peak at 264 nm is the original solution. The solid line with peaks at 565 and 614 nm is after 120 s ozonation and the dotted line is the spectrum after the discolouration from blue to pink. On top of these two curves the other more intense curves were recorded after 240 s ozonation () and after colour fading to pink ( ).

Scheme 1.

as one of the rst elementary reaction act with ozone. We have proposed a new electrophilic mechanism of

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conjugated addition across conjugated double bonds when ozone or other electrophiles [13,14] cause the addition reaction. Moreover, we have shown that it is possible to generate C60 fullerene radical cations in superacid solutions [15]. In the case of PPD, the formation of a radical cation as the rst elementary reaction step is a very well known experimental fact when the oxidizing agent is bromine in minute amounts [16]. In fact a stable radical cation, known as Wursters complex or salt is formed [16]. Of course many other dierent oxidizing agents have been tested and the reaction has been found [17,18] to be second order overall, but rst order with respect to the PPD and the oxidant. The values of the second order rate constants for the formation and the decay of the PPD radical cation were found to be in line with the oxidation potentials of the oxidant [17,18]. We have shown in a previous paper [9] that chlorine (E0 1:36 V) and ozone which are stronger oxidizing agents than bromine (in fact E0 O3 =O2 2:07 V while for E0 for Br2 =Br 1:065 V) are able to form the radical cation of PPD, provided that they are used in small amounts over the organic substrates. As shown in Scheme 1, the formation of a radical cation from a PPD derives from the one-electron oxidation of PPD. Once formed the radical cation is relatively stable but could be further oxidized to a QDI derivative by loosing another electron. It is interesting to note that the reaction between QDI and unreacted PPD leads to the formation of two radical cation molecules. This means that until in the reaction system remain a certain amount of unreacted PPD molecules, we will have a buering eect which hinder the oxidation of the radical cation to the QDI. Infact each QDI formed is

reduced back to the radical cation by the oxidation to a radical cation state of another PPD molecule. 3.1. About the ozonation of TMPPD In Fig. 1A is reported the spectrum of TMPPD 2HCl (about 1:77 104 M) in water. It is characterized by three maxima respectively at about 200 (e 13; 180), 254 (e 13; 720) and 319 nm (e 2250). These three bands correspond to the three bands of unsubstituted PPD ([19], spectrum D9/99) respectively at 197 (e 33; 500), 241 (e 9300) and 305 nm (e 1900). These bands are generated from p ! p transitions. According to Baude notation [20] the band at shorter wavelength is called E1 , followed by E2 and by the B (benzenoid)-band at longer wavelength. The intense E1 band at shorter wavelength derives from an allowed transition whereas the other two bands result from forbidden transitions in the highly symmetrical benzene molecule. In the B-band there is a contribution derived from the np interaction of the nitrogen atoms of the PPD with the p electrons of the benzene ring. When O3 is passed in the solution of TMPPD2HCl in water, a new band is observed (Fig. 1B and C). This new band shows a double peak at 562 and 610 nm and is due to the radical cation of the TMPPD [16,21] and is generated since the early reaction stages of O3 with the amine [21]. The formation of the TMPPD radical cation is accompanied also by the parallel growth of the TMPPD Bband at 320 nm (see Figs. 1B, C and 2). In fact, the 320 nm band under the action of O3 undergoes an hypschromic shift to 300 nm and increases its intensity, reaching a maximum and decreasing (see Fig. 2), following the same trend of the other bands assigned to

Fig. 2. Ozonation of TMPPD-2HCl 1:77 104 M in H2 O: evolution of the optical density of the bands associated to TMPPD (200 and 254 nm) and to its radical cation (319, 561 and 609 nm).

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the radical cation in Fig. 2. This behaviour clearly suggest that also this band is related to the formation of the radical cation and the electronic structure of the radical cation has an hyperchromic eect on the B-band of TMPPD and the PPD in general. From the literature [16] it is known that e560 11,500 while e610 11,000. By using these data and the changes in concentration of PPD as function of ozonation time, and knowing the approximate ozone amount bubbled into the reaction mixture it is possible to estimate the molar ratio between the most interesting chemical species involved. In Table 1 we have summarized our results which show that the highest molar ratio of radical cation formation over the ozone supplied occurs in the early seconds of ozonation due to the monoelectronic oxidation act which leads to the radical cation. For instance the maximum molar ratio between the concentration of the radical cation and ozone is reached after 5 s of reaction (see Table 1) and it appears that there are more than four radical cation molecules for each O3 molecules (under the assumption that all O3 bubbled into the solution has reacted). This fact gives an idea of the excellent scavenging eect of PPD towards O3 . After 5 s of reaction, 1/24 of all TMPPD molecules has already been oxidized and transformed into the radical cation (Table 1). Of course the radical cation is just an intermediate which in the case of TMPPD is relatively stable and its further oxidation is for a certain period hindered by the reducing eect of the unreacted TMPPD as discussed in Section 1 (see Scheme 1). However, as stated by Bailey [3], other competitive reactions occur in substituted tertiary PPD such as the alkyl side chain oxidation, which involves the proton abstraction mechanism. This reaction is reported to be slow and to lead, in the case of TMPPD, to N ,N 0 -dimethyl-p-quinonediimine and other products, as can be deduced from the ozonation of N,N 0 -dimethylaniline [3].

Table 1 Concentration molar ratio of the species involved in TMPPD ozonation Time (s) Radical cation/ozone (molar ratio) 0 4.4 2.5 1.4 1.1 0.8 0.6 0.3 0.05 0 TMPPD/ Ozone (molar ratio) 104 35 7 3 1.68 0.69 0.25 0.15 0.07 TMPPD/Radical cation (molar ratio) 0.0 23.8 13.7 5.1 2.9 2.0 1.2 0.9 0.5 0.0 Fig. 3. Electronic spectra of 6PPD. (A) Pure 6PPD 7:5 105 M in CHCl3 . (B) Same as in A after 15 s ozonation. (C) Same as in A after 30 s ozonation. (D) Same as in A after 60 s ozonation. (E) Same as in A after 90, 120, 180, 240, 360 s ozonation (respectively from top to bottom) in CHCl3 .

0 5 15 60 120 180 300 480 720 1200

It is also interesting to note that when the band at about 300 nm reaches its maximum concentration, the

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molar ratio between the still unreacted TMPPD and its radical cation approximates to the unity (see Table 1 and compare with Fig. 2), the TMPPD/O3 molar ratio is 0.7 and also the other radical cation bands at longer wavelength reach their maximum. From Fig. 2 it is clear that all TMPPD has been quite completely consumed after 400 s of ozonation so that the ozone attack is now directed to the oxidation of the radical cation whose concentration in fact starts to decline. As shown in Scheme 1 one of the reaction products derived from further monoelectronic oxidation of the radical cation is the QDI derivative. The ozonation of a QDI structure involves both the O3 attack to C@N double bonds as well as to C@C bonds of a quinoid structure. The general guidelines of these further degradation reactions have been discussed by Bailey [3]. When the free base TMPPD is dissolved in CHCl3 and ozonated, the blue colouration of the Wurster complex can be observed demonstrating that also in nonpolar solvents the radical cation is formed under the action of O3 . In diluted CHCl3 solution the radical cation band appears as a doublet at 565 and 614 nm, as in the case of water solution. In more concentrated CHCl3 solutions (for instance at 4:22 105 M of Fig. 1D) the radical cation band of TMPPD appear more complex with two additional features at 481 and 519 nm in addition to the other normal bands at 565 and 614 nm. In these conditions, immediately after ozonation (120 s at the usual O3 feeding rate) the solution appears blue but after the interruption of the passage of O3 , after 1 min, the solution becomes pink and the two radical cation peaks at 565 and 614 nm vanish in a band tail while the other two bands at 481 and 519 nm remain almost unchanged (see Fig. 1D). Further ozonation restores for a

short time the blue colour which turns back pink (Fig. 1D). These experimental facts suggest that in CHCl3 the TMPPD radical cation is not stable free but it forms a dimeric complex [22]. In 10% HCl solution TMPPD shows a unique maximum at 232 nm and a shoulder at 260 nm. When O3 is bubbled into the solution for 3060 s, the peak shifts to 246 nm and two new bands appear at 312 and 432 nm (broad). By further ozonation the band at 246 nm shifts back to 232 nm, hence this phenomenon indicate that in the early ozonation stages there is the formation of a charge-transfer complex between TMPPD and O3 . The band at 434 nm is due to the diprotonated radical cation. Protonation of amines typically causes the hypsochromic shift of their B-bands [20]. Thus, it is obvious to expect the radical cation band of diprotonated TMPPD lying at 434 nm instead of at 560 and 610 nm as it happens in non-acidic media. After 60 s ozonation this band is no more observable. Instead, what it has been observed is the steady growth of the band at 312 nm as function of the ozonation time and its slow shift to 306 nm. The position of this band is almost the same as observed in non-acidic water solution as described previously and it is due to the radical cation.

3.2. About the ozonation of 6PPD Contrary to the tertiary amine TMPPD, 6PPD is an N-alkylN 0 -aryl disubstituted secondary amine. It is the most widely used antiozonant for tyre application to protect the diene rubber [1]. In CHCl3 6PPD shows a maximum at 290 nm (Fig. 3A). By using 25 ml of a 6PPD solution of 7:5 105 M, after 15 s ozonation we observe the growth of a new band at 388 nm with two

Fig. 4. Ozonation of 6PPD 7:5 105 M in CHCl3 : evolution of the optical density of the band associated to 6PPD (290 nm) and to its radical cation (410 nm).

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6PPD in the solution, thanks to the mechanism of Scheme 1 which hinders the formation of the QDI derivative. This is clearly illustrated in Fig. 4 where we can observe that the rapid drop in the concentration of the 6PPD is compensated by the accumulation of the radical cation. After 60 s the radical cation starts to be degraded by O3 . Among the products there is certainly the QDI derivative which still absorb at 400 nm or at longer wavelengths, but there are also several other derivatives some of them have been identied with chromatographic techniques [23]. 3.3. About the ozonation of DPPD DPPD is another well known antiozonant. It is a diaryl-substituted PPD and it is a commercial mixture of N ,N 0 -phenyltolyl, N,N 0 -tolyltolyl and N,N 0 -diphenyl-PPD. By itself, it is not a particularly eective antiozonant in rubber compounds when used alone [1]. However, in combination with 6PPD it has sinergistic eects and ensures long protection to the rubber good [1]. In CHCl3 , DPPD shows a shoulder at 246 nm and a peak at about 300 nm (Fig. 5A). The ozonation of 25 ml of a 7:2 105 mol/l solution causes the rapid growth of the radical cation band at 411 nm (Fig. 5B, C). This band shifts slowly to 415 nm and simultaneously we observe a reduction of the band at 300 nm. By plotting the absorbance of these two bands as function of the ozonation time (Fig. 6), we get a graph which is very close to that obtained by ozonating 6PPD (compare with Fig. 4). Thus the band assignment and interpretation is analogous. The ozonation of the DPPD can be followed by the drop in optical density of the band at 300 nm. The band at 246 nm which is due to the aryl rings of the N ,N 0 -substitution survives to the ozonation and in fact the optical density of this band remains unchanged even after prolonged ozonation (see Fig. 5D). By comparing the Figs. 4 and 6 which refer respectively to 6PPD and DPPD solution of approximately equal concentration it appears evident that the maximum concentration of the radical cation occurs in both cases after about 60 s of ozonation. This is in line with literature data which show that in CCl4 the ozonation rate is equal for both PPDs [2]. However, the consumption rate of the 6PPD appears faster than that of DPPD . 3.4. About the ozonation of 6PPDTZ The antiozonant 6PPDTZ is rather new and it is nonstaining [1]. The ozonation of a CHCl3 solution 5:45 105 mol/l causes a steady reduction of the band originally lying at 297 nm. This band shifts to 275 nm after 30 s ozonation. By following this band it is possible to

Fig. 5. Electronic spectra of DPPD. (A) Pure DPPD 7:2 105 M in CHCl3 . (B) Same as in A after 20 s ozonation. (C) Same as in A after 35 s () and 50 s ( ) ozonation. (D) Same as in A after 80, 120, 150, 210 and 300 s ozonation (respectively from top to bottom) in CHCl3 .

shoulders at 410 and 480 nm (Fig. 3B). On further ozonation the shoulder at 410 nm becomes a peak and included the band at 388 nm while the shoulder at 477 nm undergoes a gradual batochromic shift to 483 nm (after 30 s, Fig. 3C) and to 500 nm (after 60 s, Fig. 3D). Additional ozonation causes a broadening of the band at 410 nm which buries the shoulder at 500 nm (Fig. 3E). The radical cation of pure unsubstituted PPD appears at 462479 nm [16] and is accompanied by a pronounced peak at 380 nm, as we have veried by ozonating pure PPD in CHCl3 . Thus it is obvious to assign the band at 388 nm with the shoulder at about 480 nm to the 6PPD radical cation. In the early stages, the ozonation proceeds with the accumulation of the

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Fig. 6. Ozonation of DPPD 7:2 105 M in CHCl3 : evolution of the optical density of the band associated to DPPD (300 nm) and to its radical cation (414 nm).

Fig. 7. Ozonation of 6PPDTZ 5:45 105 M in CHCl3 : evolution of the optical density of the band associated to 6PPDTZ (297 nm) and to its radical cation (525 nm), measured in the 1:19 104 M in CHCl3 solution.

follow the consumption of the 6PPDTZ (see Fig. 7). A more concentrated solution of 6PPDTZ (1:19 104 mol/l) shows also a B-band at 487 nm. Ozonation causes the development of a series of bands in the same spectral region having a features which recall that of ozonated TMPPD in CHCl3 . Four dierent bands appear respectively at 466, 483, 503 and 525 nm with the latter being the most intense (see Fig. 8). The position of this band is compatible with the assignment to the radical cation. The optical density of the 525 nm band is reported as function of the ozonation time in Fig. 8 for the 1:19 104 M solution. In the case of this molecule the prolonged ozonation causes the solution to become dark. It appears that ozone causes the formation of polycondensation products. The ozone attack can be directed not only to PPD groups but also to the triazine

Fig. 8. Electronic spectrum of 6PPDTZ 1:19 104 M in CHCl3 . Detail of the radical cation band after 200 s ozonation.

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Table 2 Antiozonant activity: correlations between calculations and experimental facts Molecule Enthalpy of formation of the PPD (kJ/mol) 176 126 143 196 356 420 581 Enthalpy of formation of the radical cation (kJ/mol) 571 774 793 963 1025 1094 1254 Antiozonant activity (rating) 100 95 70 60 50 35 0 Fatigue crack formation (rating) 70 100 92 75 65 50 0 Antioxidant activity (rating) 42 70 70 60 70 70 100

77PD IPPD 6PPD (6PPD)3triazine DTPD DPPD DNPD

ring although in this case the reaction speed should be slower than that with the PPD.

3.5. Discussion of the theoretical calculations and concluding remarks Although the ozonation of secondary amines leads to the formation of nitroxide radicals as the main products as shown by Razumovskii and Batashova (as cited in Ref. [3]) the general interpretation of the ozonation of the secondary aromatic PPD involve the formation of the corresponding radical cations as the rst reaction derivative [3]. Our study has conrmed the correctness of this interpretation. The experimental results reported in the previous sections have conrmed once again that all PPDs generate the respective radical cation as the rst elementary intermediate when oxidized with O3 . It has also been reported [2] that the most powerful antiozonant PPDs lead to the formation of stable radical cation intermediates while the less eective generate unstable radical cation intermediates. This led us to run some calculations according to AM1 as stated in the Experimental section. We have calculated the free enthalpy of formation of several well known PPDs reported in Table 2, the free enthalpy of formation of the radical cation and the corresponding free energy of reaction which led to the radical cation. The most surprising thing we are showing in Table 2 is that the free energy of formation of the radical cation of each PPD considered correlates with the antiozonant activity as experimentally observed in the rubber vulcanizates [24] without making any consideration on the molecular weight and diusion rate constants. More in detail, the lowest is the free energy of formation of a radical cation, and the highest is its antiozonant activity. As well known [1] N ,N 0 -dialkyl-substituted PPD are better antiozonants than N,N 0 -arylalkyl-PPD which in their turn are better than N ,N 0 -diaryl-PPD.

Thus, in principle, to design new antiozonants or to predict their antiozonant activity it could be possible for the future to apply the proposed approach which involves the calculation of the free energy of formation of the corresponding PPD.

Acknowledgements My warm thanks to Mr. Paolo Mondini for the computational calculations according to the AM1 method.

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