ISSN 0023-1584, Kinetics and Catalysis, 2017, Vol. 58, No. 5, pp. 556–562. © Pleiades Publishing, Ltd., 2017. Original Russian Text © O.T. Kasaikina, N.V. Potapova, D.A. Krugovov, L.M. Pisarenko, 2017, published in Kinetika i Kataliz, 2017, Vol. 58, No. 5, pp. 567–573.
Catalysis of Radical Reactions in Mixed Micelles of Surfactants with Hydroperoxides O. T. Kasaikinaa, b, c, *, N. V. Potapovaa, c, D. A. Krugovova, c, and L. M. Pisarenkoa aSemenov
Institute of Chemical Physics, Russian Academy of Sciences, Moscow, 119991 Russia bFaculty of Chemistry, Moscow State University, Moscow, 119991 Russia c Demidov Yaroslavl State University, Yaroslavl, 150003 Russia *e-mail:
[email protected] Received April 1, 2017
Abstract—The peculiarities of the catalytic action of cationic surfactants (CSurf) in combination with hydroperoxides on the generation of radicals and the influence of various factors on this process (transition metal compounds, oxygen, and external magnetic field) were considered. In the oxidized hydrocarbons (RH), hydroperoxides (ROOH), which are the primary amphiphilic products of oxidation, form mixed micelles {mROOH…nCSurf} with CSurf, in which fast decomposition of ROOH into radicals occurs and other polar components (metal compounds, inhibitors, etc.) can concentrate, which significantly affects the rate and mechanism of oxidation. The cationic surfactants immobilized on a solid support retain the ability to catalyze the decomposition of hydroperoxides, forming radicals, and to initiate radical oxidation and polymerization. It was found that acetylcholine, which is the most important neurotransmitter that plays an important role in the neuromuscular and cognitive activity of living beings, like cationic surfactants, catalyzes the radical decomposition of hydroperoxides in organic media, and the yield of radicals in this process decreases in a magnetic field and in the presence of oxygen. Keywords: cationic surfactants, hydroperoxides, mixed micelles, catalysis, peroxyl radicals, acetylcholine, magnetic effect DOI: 10.1134/S0023158417050093
INTRODUCTION The catalysis of chemical reactions in the presence of surfactants (Surf) is usually associated with the mechanisms of micellar [1–4] and interphase catalysis [5–8]. In the last decade, the effect of surfactants on the oxidation and stability of hydrocarbons and lipids and oil-containing food, cosmetic, and medicinal products has actively been studied in view of the opening opportunities to regulate the rate of oxidation using surfactants in new technologies [9–12]. The peculiarities of surfactant action in oxidation processes are determined by the fact that the primary products of oxidation of the majority of organic compounds are hydroperoxides (ROOH), while radicals are usually generated exactly in reactions involving ROOH (degenerate chain branching) [13–17]. In contrast to the starting oils, hydroperoxides are amphiphilic compounds and thus surfactants [18, 19]. In the oxidized substrates in the presence of surfactants, the resulting hydroperoxides form micelles mixed with surfactants {mROOH…nSurf}. The formation of mixed micelles that have a strong influence on the decomposition of ROOH was studied and confirmed by nuclear magnetic resonance (NMR) spectroscopy,
dynamic light scattering (DLS), and tensimetry [20– 22]. Inhibition [23, 24], oxidation catalysis [20, 22, 25, 26], or no effect at all [20, 24] can take place depending on the chemical nature of the surfactant and oxidized substrate. Catalytic Effect of Cationic Surfactants on the Radical Decomposition of ROOH in {mROOH…nSurf} Mixed Micelles The key reaction of the catalytic action of cationic surfactants (CSurf) on the oxidation of hydrocarbons and lipids is accelerated decomposition of hydroperoxides into radicals in mixed micelles [20–26]. With anionic and nonionic surfactants, hydroperoxides also form mixed micelles, but the radical decay is accelerated only in combination with CSurf. In micelles with CSurf, the peroxide bond obviously falls into a strong electric field of ~105–107 V/m of the electric double layer, which weakens this bond and stimulates the homolytic decomposition. Note that the micellar aggregates (mROOH + nCSurf {mROOH…nCSurf}) generated in organic media during the mixing of the cationic surfactants and hydroperoxides are thermodynamically unstable because hydroperoxides rapidly
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decompose into radicals with subsequent formation of the hydrophilic and amphiphilic products: water, alcohols, and ketones (Scheme 1), which affects the structure and size of the inverted micelles.
⎧ROOH → RO i+ HO i ⎫ ⎪ i i⎪ ⎪RO +ROOH → ROH + RO 2 ⎪ ⎪ i i ⎪ ⎨HO + ROOH → H 2O + RO 2 ⎬ i i ⎪ ⎪ → RO i 2 ⎪RO 2+ RO 2 → Products ⎪ ⎪RO i+ RO i2 → Products ⎪ ⎩ ⎭
i
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B=0 B = 150 mT
3.0
1.5 1.0 0.5 0 СТАВ, N2 CTAB, O2
(1)
The activation energy of the thermal decomposition of different ROOH is 90–120 kJ/mol [14–16]; in cationic surfactant micelles, it decreases to 40–60 kJ/mol [20, 22, 26]. Small amounts of ROOH and cationic surfactants provide significant radical generation rates (10–9–10–7 M s–1), which are inaccessible at low temperatures for known azo initiators. The generated peroxy radicals can initiate chain oxidation, polymerization, or other radical processes. In the presence of oxygen, the concentration of hydroperoxide and other polar products increases in the substrate during accelerated oxidation, which, in turn, also affects the structure and properties of the micelles. It was found that acetylcholine, an important neurotransmitter that plays an important role in the neuromuscular and cognitive activity of living beings, catalyzes the radical decomposition of hydroperoxides in organic media like cationic surfactants do [29]. Acetylcholine chloride (ACh), like many CSurf, is a quaternary ammonium salt, but, unlike the CSurf molecule, its molecule has no bulky hydrophobic substituent. ACh is highly soluble in water and has no surface activity [18]. However, when dispersed in a hydrocarbon medium together with hydroperoxides, AСh forms aggregates of the type of inverted micelles, in which the generation of radicals is accelerated [29]. A DLS analysis of the size of microaggregates that formed in an organic medium during dispersion of ACh and cationic surfactant cetyltrimethylammonium bromide (CTAB) individually and together with tert-butyl hydroperoxide (TBHP) showed that in the case of CTAB, microdispersions of ~5 μm form, whereas individual ACh does not form colloidal dispersions at all. In combination with hydroperoxides, mixed microaggregates form with a size of ~10 nm for the CTAB + TBHP mixture and 350 nm for the ACh + TBHP mixture [29]. The resulting microaggreKINETICS AND CATALYSIS
3.5
2.0
As a result of the reactions in mixed micelles (scheme), peroxy radicals are supplied into the organic solvent [27, 28]:
{m ROOH … n CSurf } → RO 2.
Wi × 109, М s–1
2.5
Scheme 1. Radical reactions that take place in {mROOH…nCSurf} micelles.
m ROOH + n CSurf
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ACh, O2
Fig. 1. Rates of radical initiation in CTAB–TBHP and ACh–TBHP systems in chlorobenzene in an inert atmosphere (in a nitrogen flow) and in air (O2) in an external static magnetic field (B = 150 mT) and in the absence of an external field (B = 0 ); total concentrations: CTAB and ACh 1.7 mM, TBHP 25 mM, β-carotene 0.01 mM. T = 37°C.
gates are basically nanoreactors in which the radicals are generated. The initiation rates of radicals (Wi) in the bulk of the organic solvent (chlorobenzene), i.e., the rates of initiation of the radical oxidation of nonpolar substrates in the bulk were measured by the inhibitors method using a nonpolar polyene hydrocarbon β-carotene as a radical acceptor [29, 30]. These experiments revealed the specific properties of radical generation in mixed micelles (Fig. 1). Oxygen and the moderate external magnetic field (magnetic induction B = 150 mT) decrease the initiation rate. In looser ACh–TBHP micelles, the initiation rates are lower than in CTAB– TBHP micelles, and the retarding effect of the magnetic field is less pronounced. Importantly, the retarding effect of the magnetic field weakens in the presence of the paramagnetic particles—oxygen and relatively stable radicals [30]. At present, much attention is paid to the study of the effects of the magnetic and electromagnetic fields on the chemical and especially biological processes [31–38]. The main contribution to the magnetic effects in biosystems can be made by processes in which radicals, radical ions, and paramagnetic particles are generated and involved, whose unpaired electrons are carriers of spin magnetism and interact with magnetic fields. The magnetic effects can show themselves only in multispin systems, when there are at least two spins, i.e., when a radical pair can form. The magnetic fields can induce spin triplet–singlet transitions in these pairs and change their spin state and reactivity [31–33]. In the CTAB–TBHP system (Fig. 1), oxygen reduces Wi by 30% and the magnetic field by 60%. In the case of larger and less ordered ACh–TBHP microaggregates, these effects are less pronounced: oxygen decreases Wi by 24% and the magnetic field by 41%. In the presence of oxygen, the effect of the external
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Table 1. Rates of O2 absorption during the oxidation of the 1 M limonene solution with additions of CTAB, ACh, and transition metals, all together or individually* Surfactant No.
Metal
without surfactant (WMe), ×106 M/s
with 1 mM CTAB (WΣ), ×106 M/s
WΣ W Me + WCTAB
with 1 mM ACh (WΣ), ×106 M/s
WΣ W Me + W ACh
1 2
Without metal Co(acac)2
1.4 6.5
4.2 25
– 2.3
4.1 4.7
– 0.4
3
Fe(acac)3
3.6
23
2.9
7.4
0.9
4
Cu(acac)2
5.5
27
2.8
15.0
1.7
5
Mn(acac)2
4.9
13.4
1.5
5.9
0.65
* Т = 60°С, [ROOH] = 40 mM, [CTAB] = [ACh] = 1 mM, and [Me] = 0.1 mM. The dash means that WΣ was not measured in these cases.
magnetic field weakens. The observed magnetic effects are anomalously large; in radical reactions, they usually do not exceed 25% [39–43]. The reason for the anomalously high magnetic effect is probably the formation of several types of diffusion radical pairs in the micellar aggregate (Scheme 1), the probability of recombination of which can be affected by the magnetic field. It is also possible that oxygen and magnetic field affect the properties of the double electric layer and the orientation of the peroxide bond, whose homolysis determines the rate of decomposition of hydroperoxide into radicals. Combined Action of Transition Metal Compounds and Surfactants on the Decomposition of Hydroperoxides The transition metal compounds often act as the homogeneous catalysts of oxidation [13–17]. The mechanism of their catalytic action is often described by the Haber–Weiss scheme, which includes the accelerated decomposition of hydroperoxide into radicals in redox reactions involving a transition metal:
ROOH + Me
n+
→ RO + Me •
n +1
−
+ HO ,
ROOH + Me n+1 → ROO• + Me n+ + H +. The catalytic activity of the compound strongly depends on the nature of the metal, ligand, and hydroperoxide. In organic media (inverted water-inoil (W/O) systems), when the polar components are concentrated inside and/or at the micelle–medium interface, the catalytic action of CSurf and metal compounds can be synergetic [26, 44]. For oxidation of ethylbenzene used as an example [44], it was shown that combination of relatively small concentrations of cationic CTAB and cobalt acetylacetonate (Co(acac)2) allows high rates and almost selective oxidation of ethylbenzene into the carbonyl derivative acetophenone. The rates of oxygen absorption during the oxidation of the natural olefin limonene catalyzed by Co(II), Mn(II), Fe(III), and Cu(II) acetylacetonate additions in combination with mixed microaggregates
formed by CTAB and ACh with hydroperoxide limonene (ROOH) are presented in Table 1. All acetylacetonates taken individually accelerate the oxidation. The strongest catalyst is Co(acac)2. In a mixture with CTAB, all acetylacetonates exhibit synergism, i.e., the absorption rate of O2 in the presence of both the metal compound and CTAB (WΣ) is much higher than the sum of the oxidation rates with these additions taken separately (WMe + WCTAB). The synergism is most pronounced for the Fe(acac)3 + CTAB system. The combined effect of metal compounds and CTAB in limonene differs from that of these catalytic systems in the oxidation of ethylbenzene. In ethylbenzene, the most active system was the CTAB–Co(acac)2 combination [44], whereas the iron compounds showed no appreciable activity when taken individually or in combination with CTAB. When ACh is present together with the metal compounds, the opposite picture is observed: WΣ < WMe + WACh. When Co(acac)2 is added together with ACh, the oxidation rate is even lower than in the presence of Co(acac)2 alone, i.e., Co(acac)2 and ACh are mutually deactivated. Only in the case of Cu(acac)2, oxidation develops at the highest rate at the beginning, which exceeds that of WMe + WACh more than 1.5-fold. However, after 10 min, WΣ decreases sharply, and the oxidation changes into the stationary mode at a rate equal to the rate of O2 absorption in the absence of ACh. Apparently, the additions of metal compounds immediately destroy the microaggregates formed by acetylcholine. Perhaps in the case of Cu(acac)2, an active complex with ACh is formed, which is rapidly deactivated during the oxidation. A detailed study of the oxidation kinetics of limonene [26] with CTAB and Co(acac)2 additions (Table 1) taken individually and in a mixture demonstrated that the synergism index, the WΣ/(WMe + WCTAB) ratio, increases with the limonene concentration from 2.34 in the 1 M solution to 3.6 in the 2 M solution and 6.4 in undiluted limonene (at 60°C). The temperature dependence of the radical initiation rate evaluated KINETICS AND CATALYSIS
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from the chain oxidation rate showed that the activation energy of ROOH decomposition in the presence of CTAB is low (ECTAB = 27 kJ/mol), while the activation energies of ROOH decomposition in the presence of individual Co(acac)2 (ECo = 75 kJ/mol) and in a mixture of Co(acac)2 and CTAB (EΣ = 73 kJ/mol) are close. In this case, it can be assumed that the observed synergism in ROOH decomposition is due to the concentration of Co(acac)2 and ROOH in mixed microaggregates, and the decomposition of ROOH catalyzed by Co(acac)2 becomes the limiting stage of the whole process. As a result of the accelerated decomposition of limonene hydroperoxide in mixed micelles, increased yield of carvone, a valuable carbonyl derivative of limonene formed during the disproportionation of radicals, is observed along with the increased rate (Scheme 1). Thus, combination of CSurf with metal compounds is a promising basis for creating the catalytic systems for the production of carbonyl compounds by oxidation of hydrocarbons with air oxygen. Catalysis of the Radical Decomposition of Hydroperoxides by Heterogeneous Catalysts Obtained by Immobilizing CSurf on Solid Supports In recent decades, research and practical applications in the field of synthesis and technology for the production of polymer composite materials with layered silicates used as a filler have actively been developed [45–50]. To combine aluminosilicates with nonpolar polymers, their surface is hydrophobized with CSurf Cl–N+, mainly with the alkyl derivatives of quaternary ammonium salts. It was of interest to examine whether the CSurf immobilized on the surface of layered silicate or other support retains its ability to “attract” hydroperoxides and accelerate their homolytic decay into radicals or not. This method for radical generation could be used to prepare nanocomposites by radical polymerization of vinyl monomers initiated directly from the filler surface. Moreover, for practical purposes (for oxidation), heterogeneous catalysts that can be separated from the reaction products are more convenient. Figure 2 shows the data of the trials of the commercial sodium montmorillonite samples hydrophobized with CSurf, namely, the data on their effect on the oxidation rates of limonene containing 50 mM hydroperoxide: 1. Starting montmorillonite (10% < 2μk, 50% < 6μk, 90% < 13μk), CloisiteNa (United States). 2. Cloisite 20A modified with Cl–N + (CH3)2(C18– C16)2 (United States). 3. Cloisite 93A modified HSO 4− N+(CH3)2(C18– C16)2 (United States). 4. CloisiteNa on which the monomolecular layer of CTAB was adsorbed. KINETICS AND CATALYSIS
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WO 2 × 10 7, М s–1 9 8 7 6 5 4 3 2 1 0 0
1
2
3
4
Fig. 2. Effect of clay samples on the rate of oxidation of 1 M limonene in a chlorobenzene solution containing 50 mM ROOH in the presence of clay samples (50 mg/mL) without additives (0) and with additives (see text) (1–4). T = 37°C.
The oxidation rate in the absence of additives characterizes the process initiated by the thermal decomposition of 50 mM limonene hydroperoxides. Untreated CloisiteNa increases the oxidation rate. Samples (2) and (4) increase the oxidation rates to the greatest extent. It is noteworthy that the sample (3) modified with CSurf with a counterion accelerates the oxidation of limonene even to a lesser extent than the starting CloisiteNa. It was found [18, 20, 22] that the activity of CSurf in accelerating the decomposition of hydroperoxides depends on the counterion and decreases in the sequence Cl– > Br– > HSO 4− for cetyltrimethylammonium salts. According to Fig. 2, the nature of the CSurf counterion used for hydrophobization of aluminosilicate is also important for initiating the radicals in the hydrophobized aluminosilicate–hydroperoxide system, although it was assumed that the counterions and sodium cations are removed together with water during hydrophobization by ion exchange. It also follows from Fig. 2 that CSurf adsorbed on CloisiteNa retains its ability to catalyze the radical decomposition of hydroperoxides.
Since the mixed {mROOH…nCSurf} micelles provide peroxyl radicals in the bulk, it was doubtful whether the cationic surfactants immobilized on the support surface could be used for initiating the radical polymerization. As solid supports, finely disperse substances were taken which are used as additive fillers in the synthesis of composite materials: clay (sodium montmorillonite) [45–49] and microcrystalline cellulose [50–53]. The efficiency of the obtained colloidal catalysts in generating the radicals in a medium containing hydroperoxide was tested in the radical chain
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Table 2. Adsorption of СТАВ and АСh and radical generation rates measured during the oxidation of limonene (2 М) in a chlorobenzene solution containing ROOH (0.2 М) and 4.7 wt % catalyst and during polymerization of styrene containing 0.05 М cumyl hydroperoxide and 4 wt % catalyst at 60°C Catalyst
Adsorption of surfactant, Γ × 10 4, mol/g
Wi × 107, mol/(L s) limonene oxidation
Wi × 107, mol/(L s) styrene polymerization
– 5.70 1.85 12.2 8.0
0.58 2.4 12.9 11.5 5.8
0.42 0.76 7.60 1.1 2.0
– СТАВ/М СТАВ/Cel АСh/М АСh/Cel
Γ is the specific adsorption of a substance on the support, mol/g. The dash means that heterogeneous catalysts were not added to limonene and styrene containing the corresponding hydroperoxides; initiation was only due to the decomposition of hydroperoxides.
Table 3. Total concentrations of СТАВ and ACh and specific radical generation rates during the oxidation of 1 М limonene and styrene polymerization* No.
Catalyst
[Surfactant]s, mM
ϖ i × 10 4, М s–1
[Surfactant]s, mM
styrene polymerization 1 2 3 4 5 6
СТАВ СТАВ/М СТАВ/Cel ACh ACh/M ACh/Cel
1 21.3 10.5 – 45 29
38 1.5 16.0 – 0.3 1.1
ϖ i × 10 4, М s–1
limonene oxidation 1 28.5 9.25 1.5 57 37
38 0.32 6.3 8.5 0.96 0.7
* [ROOH] = 0.05 M, Т = 60°C. The dash means no data.
oxidation of limonene and radical polymerization of styrene containing cumyl hydroperoxide. The heterogeneous catalysts of the radical decomposition of hydroperoxides (CTAB/M and ACh/M) were prepared by adsorption of CTAB and acetylcholine chloride (ACh) on sodium montmorillonite (CloisiteNa, USA), and the CTAB/Cel and ACh/Cel catalysts were obtained by adsorption of CTAB and ACh on microcrystalline cellulose (Evalar, Russian Federation) (Table 2). The rates of chain oxidation and polymerization (W) are described by the equation [13–15] (2) W = a [RH] ⋅ W i 0.5, 0.5 where Wi is the rate of initiation, a = kp/(2kt) is the ratio of the rates of chain propagation (kp) and termination (kt). As kp and kt are known for both processes [13, 54], the initiation rate was calculated by the equation (3) Wi = {W/(a[RH])}2. The efficiency of the supported catalyst depends both on the value of adsorption of the active substance (Γ) and on the effect of the support on its activity. To compare the effect of the support on the activity of CTAB and ACh in radical generation, we used a parameter similar to the specific rate of radical initiation and equal to ϖ i = (Wi – W0i)/([ROOH][Surf]s),
where Wi and W0i are the rates of radical generation with a catalyst and without it; [Surf]s is the total concentration of the surfactant that is introduced in the reaction mixture in the catalyst. The highest activity in the decomposition of hydroperoxide into radicals is shown by CTAB and ACh in micelles mixed with ROOH (Table 3). Adsorption on a solid support evidently hinders the access of hydroperoxide to the altered double electric layer, which leads to a decrease in the radical generation rate. The relatively low value of CTAB/M may be due to the substrate effect on the heterolytic decomposition of hydroperoxide. Thus, when a solution of cumyl hydroperoxide with a montmorillonite addition was allowed to stay, the decay products contained phenol, which formed as a result of the heterolytic decomposition of alkylaromatic hydroperoxides on sulfates, phosphates [20, 23], and obviously aluminosilicates. Radical polymerization of unsaturated compounds initiated by the cationic surfactant adsorbed on the support surface by generating the radicals on the surface of the solid support opens up an opportunity of creating polymer coatings. Thin films were obtained on flat glasses with an adsorption layer of CTAB or ACh, which were immersed for 2 h in styrene containing tert-butyl hydroperoxide [55]. The surface analysis was performed by the AFM method, which allows a KINETICS AND CATALYSIS
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quantitative study of the film thickness and quality, namely, the distribution of mechanical properties such as Young’s modulus, adhesion, and local deformation. It turned out that islands of a polystyrene film with a Young’s modulus characteristic for polystyrene formed on the surface of glass with a thickness of up to 60 nm. CONCLUSIONS To summarize, CTAB and ACh are well sorbed on cellulose and montmorillonite and retain their catalytic activity in the decomposition of hydroperoxides into radicals. These results can find various applications for creating bactericidal, disinfectant, and medical materials based on supports, which, like sodium montmorillonite and cellulose, bear a negative charge that stimulates the adsorption of cationic surfactants. ACKNOWLEDGMENTS This study was financially supported by the Russian Scientific Foundation (grant no. 14-23-00018). REFERENCES 1. Berezin, I.V., Martinek, K., and Yatsimirskii, A.K., Usp. Khim., 1973, vol. 42, no. 10, p. 1729. 2. Dynamics of Surfactant Self-Assemblies: Micelles, Microemulsions, Vesicles, and Lyotropic Phases, Zana, R., Ed., Boca Raton: CRC, Taylor and Francis Group, 2005. 3. Khan, M.N., Micellar Catalysis, Surfactant Science Series, vol. 133, Boca Raton: CRC, Taylor & Francis, 2006. 4. La Sorella, G., Strukul, G., and Scarso, A., Green Chem., 2015, vol. 17, p. 644. 5. Fendler, E.J. and Fendler, J.H., Adv. Phys. Org. Chem., 1970, vol. 8, p. 271. 6. Demlow, E. and Demlow, S., Phase Transfer Catalysis, Weinheim, Germany: Chemie, 1983. 7. Cornils, B. and Hermann, W.A., Applied Homogeneous Catalysis with Organometallic Compounds, Weinheim, Germany: Wiley–VCH, 1996. 8. Lindner, E., Schnellert., Auer, F., and Mayer, H.A., Angew. Chem. Int. Ed., 1999, vol. 38, p. 2154. 9. Kittipongpittaya, K., Panya, A., Cui, L., McClements, D.J., and Decker, E.A., J. Am. Oil Chem. Soc., 2014, vol. 91, p. 1955. 10. Chen, B., McClements, D.J., and Decker, E.A., Crit. Rev. Food Sci. Nutr., 2011, vol. 51, p. 1080. 11. Decker, E.A. and Storeys, M.L., Adv. Nutr., 2015, vol. 6, no. 3, p. 288. 12. Laguerre, M., López-Giraldo, L.J., Lecomte, J., Figueroa-Espinoza, M.-C., Baréa, B., Weiss, J., Decker, E.A., and Villeneuve, P., J. Agric. Food Chem., 2010, vol. 58, p. 2869. 13. Emanuel', N.M., Denisov, E.T., and Maizus, Z.K., Tsepnye reaktsii okisleniya uglevodorodov v zhidkoi faze (Chain Liquid-Phase Oxidation Reactions of Hydrocarbons), Moscow: Nauka, 1965. KINETICS AND CATALYSIS
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Translated by L. Smolina
KINETICS AND CATALYSIS
Vol. 58
No. 5
2017
