WO2007042175A1

WO2007042175A1 - Peroxide decomposition catalyst

Info

Publication number: WO2007042175A1
Application number: PCT/EP2006/009572
Authority: WO
Inventors: Johan Franz Gradus Antonius Jansen; Engelina Catharina Kleuskens; Ivo Ronald Kraeger
Original assignee: Dsm Ip Assets B.V.
Priority date: 2005-10-07
Filing date: 2006-10-02
Publication date: 2007-04-19

Abstract

This invention relates to a method for the catalytic decomposition of peroxides, wherein the peroxide is decomposed by means of one or more dioxo- compounds selected from the group of diketones, dialdehydes or ketoaldehydes having a calculated reduction energy (CRE) in the range of from -10 to -30 kcal/mole, the CRE being the energy difference in kcal/mole between the lowest energy conformations of the radical anion and the corresponding neutral molecule as calculated by means of the Turbomole Version 5 program. The present invention also relates to the formation of radicals by means of catalytic decomposition of peroxides using any of such dioxo-compounds. The radicals so formed can suitably be applied in any application selected from the group of radical polymerizations, grafting reactions, bleaching, drying of alkyds, epoxidation reactions, sterilization processes, and desinfection processes.

Description

PEROXIDE DECOMPOSITION CATALYST

This invention relates to novel methods for catalytic decomposition of peroxides. The present invention also relates to the formation of radicals by means of catalytic decomposition of peroxides.

Catalysts, which can decompose peroxides, and in particular catalysts, which can decompose hydrogen peroxide into oxygen and water, are well known for propulsion purposes, such as, for instance, in submarines and torpedoes. Reference, for instance, can be made to US-A-3,019,197. A special type of application of decomposition of peroxide is in jet engines, as can be seen, for instance, from US-A-3, 363,982. Generally the known catalysts for peroxide decomposition are transition metals or transition metal based compounds.

Catalytic decomposition of peroxides is also used, for instance, in sterilizing of desinfection tools, contact lenses, etc. with peroxide solutions such as aqueous hydrogen peroxide. An example of such a sterilizing process with catalytic decomposition of hydrogen peroxide by means of a platinum catalyst can be found in DE 19522950. A sterilizing device using manganese, iron or copper salts or complexes for catalytic decomposition of hydrogen peroxide is described in EP-A-0882492.

For many applications where peroxides need to be decomposed, the use of transition metals or transition metal based compounds is, however, undesirable due to their environmental impact. This has resulted in development of other methods for decomposition of peroxides by means of enzymes as is, for instance, described in US-A-5362647. Enzymes, however, are only active in water (or aqueous media) within a fixed, and rather narrow, pH range (for each individual enzyme). Moreover, they generally cannot be applied in organic solvents.

Accordingly, there is need for novel methods for catalytic decomposition of peroxides, especially for catalytic decomposition of hydroperoxides, which are not based on transition metals or transition metal based compounds. It is noted, that diacylperoxides such as benzoylperoxide (BPO) can be decomposed by the action of amine compounds, but such decomposition mechanism is not effective for other peroxides than diacylperoxides. Hydroperoxides, for instance, cannot be decomposed using amine compounds alone.

Surprisingly the inventors now have found that a wide range of organic dioxo-compounds can suitably be used as catalyst for the decomposition of peroxides. In particular, the inventors now have found a novel and surprising method for the catalytic decomposition of peroxides, wherein the peroxide is decomposed by means of one or more dioxo-compounds having a calculated reduction energy (CRE) in the range of from -10 to -30 kcal/mole, the CRE being the energy difference in kcal/mole between the lowest energy conformations of the radical anion and the corresponding neutral molecule as calculated by means of the Turbomole Version 5 program.

Many dioxo-compounds are falling within the said range of CRE- values. Suitable examples of such dioxo-compounds are the ones shown in table 3 of the experimental part, namely, for instance, pyruvic aldehyde, camphoquinone,

2,3-hexanedione, 3,4-hexanedione, 2,3-pentanedione, and 2,3-butanedione, but many other dioxo-compounds will have CRE-values in the said range. Other dioxo- compounds, for instance 3,5-dk-butyl-1 ,2-benzoquinone, benzil, oxalic acid, pyruvic acid, diethyl oxalate, acetylacetone, methylacetoacetate and dimethylacetoacetamide, however, have CRE-values well outside the said range. For instance, acetylacetone, a substance often used in combination with cobalt for achieving curing of unsaturated polyesters according to the state of the art (e.g. see Kolczynski et al. in the proceedings of the 24^th Annual Technical Conference SPI (The Society of the Plastics Industry, Inc.), 1969, Reinforced Plastics/Composites Division, at Section 16-A pagesi -8) has a CRE-value of +4, 16 kcal/mole.

It is preferred in the method for the catalytic decomposition of peroxides according to the invention, that at least one dioxo-compound of the one or more dioxo-compounds has a CRE in the range of from -10 to -20 kcal/mole. Most preferably, the one or more dioxo-compounds each have a CRE between -13 and -17 kcal/ mole.

The decomposition of the peroxide can be accomplished using one single dioxo-compound as catalyst, but it can also be done using a mixture of such dioxo-compounds. In a specific embodiment of the invention, in the decomposition of the peroxide at least one dioxo-compound of the one or more dioxo-compounds is a vicinal dioxo compound. 2,3-Hexanedione, 3,4-hexanedione, 2,3-pentanedione and butanedione are suitable examples of such vicinal dioxo-compounds, but the groups next to the oxo-groups also may be longer than C_{1 or 2}-groups and the oxo-groups do not need to be ketone groups. They also may be aldehyde groups, or part of a carboxylic group or an amide group. Preferably, at least one of the oxo-groups in the vicinal dioxo- compound is a ketone group. More preferably, the vicinal dioxo-compound is a vicinal diketone. Most preferably, at least one of the ketone groups in the vicinal dioxo- compound is a methyl ketone. Accordingly, from the above list of dioxo-compounds 2,3-hexanedione, 3,4-hexanedione, 2,3-pentanedione and butanedione are most preferred.

The inventors have further found that the decomposition of a peroxide is strongly accelerated by the addition of a base or a mixture of bases. Accordingly, in a preferred embodiment of the invention, the catalytic decomposition of peroxides is achieved by means of one or more dioxo-compounds in combination with a base or a mixture of bases. Preferably, the said base is either an organic or inorganic oxide, hydroxide, alkoxide or carboxylate of which the cation has a redox potential of the metal of at most -1 V, or is an ammonium ion; and/or a nitrogen containing organic compound; or any mixture of such bases.

As meant herein, the term "redox potential of the metal" refers to the values, in V (Volt), for the transition Mⁿ⁺ to M (wee versa), for any specific metal M. These values can be found in CRC Handbook of Chemistry and Physics, 84^th Edition (2003-2004) in Section 8, Electrochemical Series, table 1 , pages 8-23 to 8-27, CRC Press LLC, Boca Raton / London / New York / Washington, D.C. For convenience, some redox potentials for metals are given below for a number of elements, the redox potentials (in V) shown between brackets: Li (-3,0), Na (-2,7), K (-2,9), Rb (-2,9), Cs (-2,9), Be (-1 ,7), Mg (-2,4), Ca (-3,0), Sr (-2,9), Ba (-2,9), Sc (-2,1), Y (-2,4), Al (-1 ,7). All these metals are examples of suitable metals with cations having a redox potential of the metal of at most -1 V. Metals falling outside the abovementioned range of at most -1 V are, for instance: Cr (-0,6), Co (-0,3), Fe (-0,4), Pt (+1 ,2), Ni (-0,2) and Cu (+0,3).

Suitable carboxylates are, for instance, acetates, benzoates, butyrates, propionates, adipates, mono-/di-/tri-chloroacetates, mono-/di-/tri- fluoroacetates, naphthenates, neodecanoates, valerates, oleates, stearates, tartrates, ascorbates, succinates, maleates, fumarates, phthalates, citrates, acrylates, methacrylates, itaconates, gluconates, glutarates, etc.). Suitable alkoxides are, for instance, methoxide, ethoxide, propoxide, butoxide, t-butoxide, phenolate, etc.

Needless to say, that the lists of suitable cations, amines, carboxylates and alkoxides can be extended much more, and that the number of possible combinations thereof leads to even larger lists. It is to be noted that US-A-3398213 ('213) teaches the curing of - A -

unsaturated polyester resins with ketone peroxides by means of cobalt salts in the presence of dioxo-compounds. In the examples of '213 (see Ex.3) it can be seen, that curing with 2,3-butanedione is less favorable than with 2,4-pentanedione. This document '213, however, does not teach anything about such curing without cobalt salts and, moreover, shows curing with 2,4-pentanedione. The latter compound, however, cannot be used for the decomposition of peroxides according to the present invention. US-A-3653954 ('594) shows that unsaturated polyester resins can be cured with peroxides and cobalt salts, for instance in the presence of 2,4-pentanedione (see Ex. I and Ex. V). Presence of cobalt salts, however, is undesirable in view of environmental aspects. None of these references '213 and '594 teaches that curing can be performed with 2,3-butanedione alone. '213 even teaches away from using 2,3-butanedione.

More preferably, the cation of at least one of the bases has a redox potential of at most -1 ,5 V. In one preferred embodiment of this embodiment of the invention, at least one of the bases is an inorganic base. More preferably, at least one of the bases is an organo-soluble base. Excellent results are achieved if at least one of the said bases is based on an alkaline or earth alkaline metal, or is an ammonium salt.

Suitable examples of such metal ion cations already have been shown above, together with their redox potential values of the metal. . Suitable examples of ammonium ions can be represented by the general formula R¹R²R³R⁴N⁺, wherein R¹, R², R³, and R⁴ each individually may represent hydrogen (H), or a CrC₂₀ alkyl, aryl, alkylaryl or arylalkyl group, that each optionally may contain one or more hetero-atoms (e.g. oxygen, phosphor, nitrogen or sulphur atoms) and/or substituents. The groups may be linear, or branched; they also may contain one or more unsaturations or substituents. Merely by way of example such ammonium ions might be, for instance, mono-, di-, tri-, or tetra-methylammonium; mono-, di-, tri-, or tetra-ethylammonium; mono-, di-, tri-, or tetrabutylammonium; trimethylbenzyl-ammonium; dimethylbenzylammonium; mono-, di-, tri-, or tetraoctylammonium; hydroxylammonium; hydrazonium; etc. R¹ in the above formula can also be selected from the group of -OR² and -NR²R³ groups, R² and R³ having the same meaning as described above.

Suitable examples of nitrogen containing compounds to be used as bases in the resin compositions according to the invention are ammonium oxides, hydroxides and alkoxides. Examples of the ammonium ions already have been listed above. Other suitable examples of nitrogen containing compounds (in principle non- ionic, but possibly becoming positively charged in situ; the nitrogen compound then can be present in the form of a salt) can be represented by the general formula R¹R²R³N, wherein R¹, R², and R³ each individually may have the meaning as described above. This general formula R¹R²R³N also represents nitrogen compounds, wherein the nitrogen atom shown in the formula is part of a cyclic system formed by two of the groups R¹, R², and R³, or is present in the form of an imine group or as a phosphazene (in which latter cases the general formula in fact can be represented as R¹R²N). Of course, R¹, R², and R³ themselves also individually may contain additional nitrogen atoms. Merely by way of example such nitrogen containing compounds might be chosen, for instance, from 1 ,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU);

1 ,4-diazabicyclo-[2,2,2]-octane (DABCO); 1 ,5-diazabicyclo-[4,3,0]-non-5-ene (DBN); morpholine; piperidine; dimethylaniline; N,N-di-isopropanol-toluidine (DiPT); hydroxylamine; alkylhydrazides; alkylhydrazines; imines (e.g. benzylidenephenylamine; N-[(E)-ethylidene]-2-methylpropanamine; 5-methyl-1 -pyrroline; 2,4,4-trimethyl-2-oxazoline; 4-phenylimino-2-pentanone); phosphazenes (e.g. compounds known as P₄-t-Bu and P₄-t-Oct); etc.

It is specifically preferred, that at least one of the said bases is a Li, Na or K base.

It is further preferred, in another specific embodiment of the invention, that at least one of the bases is an amine compound. In such case, at least one of the bases preferably is a tertiary amine compound.

The method for decomposition of peroxides according to the invention can be used for cleaving all types of peroxides.

The peroxides used for the initiation can be any peroxide known to the skilled man, for instance the wide group of peroxides that is being used in curing of unsaturated polyester resins and vinyl ester resins. Such peroxides include organic and inorganic peroxides, whether solid or liquid; also hydrogen peroxide as well as hydrogen peroxide adducts like percarbonates and perborates may be applied. Examples of suitable peroxides are, for instance, peroxy carbonates (of the formula -OC(O)O-), peroxyesters (of the formula -C(O)OO-), diacylperoxides (of the formula -C(O)OOC(O)-), dialkylperoxides (of the formula -00-), etc. They can also be oligomeric or polymeric in nature. An extensive series of examples of suitable peroxides can be found, for instance, in US 2002/0091214-A1 , paragraph [0018]. The skilled man can easily obtain information about the peroxides and the precautions to be taken in handling the peroxides in the instructions as given by the peroxide producers. Particularly suitable are the peroxides chosen from the group of hydrogen peroxide and organic peroxides. Examples of such suitable organic peroxides are: tertiary alkyl hydroperoxides (such as, for instance, t-butyl hydroperoxide), and other hydroperoxides (such as, for instance, cumene hydroperoxide), the special class of hydroperoxides formed by the group of ketone peroxides (such as, for instance, methyl ethyl ketone peroxide and acetylacetone peroxide), peroxyesters or peracids (such as, for instance, t-butyl peresters, benzoyl peroxide, peracetates and perbenzoates, lauryl peroxide, including (di)peroxyesters), perethers (such as, for instance, peroxy diethyl ether). Often the organic peroxides used as curing agent are tertiary peresters or tertiary hydroperoxides, i.e. peroxy compounds having tertiary carbon atoms directly united to an -OO-acyl or -OOH group. Clearly also mixtures of these peroxides with other peroxides may be used in the context of the present invention. The peroxides may also be mixed peroxides, i.e. peroxides containing any two of different peroxygen-bearing moieties in one molecule). It will be evident that the present invention can also suitably be used for the decomposition of peroxides, which are being formed in situ under the influence of oxygen present in a reaction medium and/or in contact therewith.

The inventors have found that the present invention is particularly useful for the catalytic decomposition of peroxides from the group of hydrogen peroxide, hydroperoxides and ketone peroxides. More preferably, the peroxide is a liquid or dissolved peroxide compound. Most preferably, the peroxide is a liquid or dissolved hydroperoxide compound.

Most suitably, the decomposition of peroxides according to the present invention is carried out in a liquid medium. Finally the present invention relates to a method for the production of radicals formed by decomposition of a peroxide (according to the methods for decomposition of peroxides as claimed herein), and use of the radicals formed thereby in an application selected from the group of radical polymerizations, grafting reactions, bleaching, drying of alkyds, epoxidation reactions, sterilization processes, and desinfection processes. Examples of processes wherein the present invention will be able to find suitable application, are, for instance, delignification processes and subsequent bleaching processes in the paper industry (where state of the art processes need to be carried out in the presence of oxygen, and under conditions of high pressure and high temperature; the present invention will make it possible to carry out such processes at lower temperature and milder conditions of pressure); or the removal of remaining peroxides after peroxide-assisted processes have taken place, for instance, in the textile industries (according to the present state of art such removal of remaining peroxides is done by using catalase enzymes; the present invention enables such removal without addition of enzymes). The invention is further illustrated by the following examples and comparative experiments without being restricted to the specific examples shown.

Calculated Reduction Energy (CRE)

For each dioxo-compound, for which the Calculated Reduction Energy needs to be assessed, the following procedure is to be followed:

In a first step, for any of such dioxo-compounds, the neutral molecule and its corresponding radical anion are constructed by means of the builder facilities of the Spartan Pro package (version 1.03; January 2000) from Wavefunction Inc. (18401 Von Karman Ave., Suite 370, Irvine, CA 92612, United States of America). The package used in said first step, then subsequently is used for performing initial geometry optimizations and conformational analyses at the so-called AM1 level.

Next, for each dioxo-compound studied, except for the AM1 structures containing internal hydrogen bonds, all AM1 structures having a relative energy of 0 - about 4 kcal/mole with respect to the AM1 global minimum, are used as input for carrying out density functional calculations by means of the Turbomole program (Turbomole Version 5, January 2002 from the Theoretical Chemistry Group of the University of Karlsruhe, Germany, as developed by R. Ahlrichs et a/.). These Density Functional Turbomole (DFT) optimizations are performed with the Becke Perdew86 functional "BP86" as is described in the combined papers of A. Becke (Phys. Rev. A, 1988, 38, p.3098-3100) and J. Perdew (Phys. Rev. B, 1986, 33, p.8822-3824), in combination with the standard SV(P) basis set (as described by A. Schafer et a/., J. Chem. Phys., 1992, 97, p.2571-2577) and the so-called Rl (Resolution of Identity) algorithm (as described by K. Eichkom et a/., Theor. Chem. Ace. 1997, 97, p.119-124) employing default convergence criteria of 10^'6 a.u. (atomic units) for the maximum energy change and of 10^'3 a.u. for the maximum gradient. Accordingly, all calculations relating to the radical anions, involve the unrestricted open-shell spin wavefunctions. The BP86/SV(P) method used here, in combination with the Rl algorithm in the Turbomole program, is unambiguously defined for the skilled user of the Turbomole program. From the BP86/SV(P) global minima so obtained, subsequently the electron affinity (EA) is determined for each of individual dioxo-compound X studied, by means of formula (2):

EA(X) (kcal/mole) = (E_totai(radical anion of X) - E_totaι(X) )^*627.51 formula (2)

with E_to_tai denoting the BP86/SV(P) global minima total energies in a.u., respectively for the radical anion and for the neutral molecule of the dioxo-compound X.

The electron affinity so determined is, in the context of the present application, referred to as Calculated Reduction Energy (CRE), in kcal/mole.

For some specific CRE values also please refer to table 3, below.

Example 1

To 2 g of Butanox M50 (a ketone peroxide peroxide solution of Akzo Nobel, the Netherlands) was added 0.2 g of butanedione. Immediately the decomposition of the peroxide started, as could be seen from the quick temperature increase. The mixture started boiling vigorously and the temperature rose to above 123 ⁰C.

Example 2

To 2 g of hydrogen peroxide (33% in water) was added 0.2 g of 2,3-pentanedione. Immediately decomposition of the peroxide started, as could be seen from the quick temperature increase. The reaction mixture started boiling vigorously and the temperature rose to above100 ⁰C. A safer method to demonstrate the peroxide decomposition is to use it as initiator in a radical polymerization. For these experiments radical polymerization in unsaturated polyester (UP) resin manufacture was used as a model reaction. Herein the following resin (Resin A) was used:

Preparation of Resin A

184.8 g Of propylene glycol (PG), 135.8 g of diethylene glycol (DEG), 216.1 g of phthalic anhydride (PAN), 172.8 g of maleic anhydride (MAN), and 200 ppm of hydroquinone (benzene-1 ,4-diol) as inhibitor, were charged into a vessel equipped with a reflux condenser, a temperature measurement device and an inert gas inlet. The mixture was heated slowly to 205 ^CC. At 205 ⁰C the mixture was kept under slightly reduced pressure until the acid value reached a value below 16 mg KOH/g of resin and the falling ball viscosity at 100 ⁰C was below 50 dPa.s. Then the vacuum was relieved with inert gas, and the mixture was cooled down to 130 ⁰C, whereafter the solid UP resin so obtained was transferred to a mixture of 395 g of styrene and 0.07 g of mono- t-butyl-hydroquinone and was dissolved at a temperature below 80 ⁰C.

Example 3. a (3.1 and 3.2)

To 40 g of resin A was added 0.4 g butanedione, followed by 1.2 g of a peroxide as indicated in table 1. The decomposition of the peroxide was monitored with a thermocouple and the peak time and peak temperature are shown in table 1 : Table 1

Trigonox 44B is a peroxide, available from Akzo Nobel, the Netherlands.

Examples 3.b (3.3 to 3.8) To 40 g of resin A was added 0.4 g butanedione and 0.05 g of potassium octanoate, followed by 1.2 g of a peroxide (all being commercially available from Akzo Nobel, the Netherlands) as indicated in table 2. The decomposition of the peroxides was monitored with a thermocouple and the peak time and peak temperature are shown in table 2: Table 2

These examples demonstrate that a large variety of peroxides can be decomposed according to the invention. Moreover, comparison of the examples 3.1 with 3.3, respectively 3.2 with 3.4, demonstrate that the addition of a base (i.e. potassium octanoate) further increases the rate of peroxide decomposition. Example 4 and Comparative Example A

90 g Of resin A was mixed with 10 g of styrene, followed by addition of 1 wt.% of a dioxo-compound as indicated in table 3 below, and of 67 mg of a 50% aqueous KOH solution (i.e. 6 mmol of KOH/kg of resin). After stirring for about 5 min, 3 g of peroxide (Butanox M50) was added and the resin was allowed to cure. Effect of curing was evaluated qualitatively by assessing whether a solid resin material was obtained after 24 hr, or whether the resin still remained liquid after 24 hr, as shown in Table 3: Table 3

In this table:

++ means hard solid material obtained after 2 hr;

+ means solid material obtained after 24hr; means remains liquid after 24 hr.

These experiments demonstrate clearly that dioxo compounds with a CRE between -3 and -34 kcal/ mol can be used as catalysts for the decomposition of peroxides.

Example 5 and comparative experiments B-C

600ml Of tea (earl grey) was prepared in 5 minutes and then cooled down quickly to room temperature. The tea was then divided into twelve portions of 50 ml each, and several bleaching catalysts were added to the various portions at the same moment. The color of the tea was determined by means of its Garden Color values (GC-values at specific t=x, using a Dr Lange LICO^®50 (Paul N. Gardner

Company, Texas, USA) color measurement apparatus suitable for transparent liquids.

The bleaching of the tea was calculated according to the formula shown below:

1-GC_t=_x/GC_t=o in %.

wherein GC_t=x represents the Garden Color value at t=x.

The higher the Garden Color value obtained, the better the bleaching of the tea.

The results are shown in table 4: Table 4

In this table: BD=butanedione PPD= phenylpropanedione NaAc= sodium acetate H₂0₂=hydrogen peroxide, 33% in water

These experiments and the comparative examples demonstrate that the decomposition of peroxides according to the invention can be used for bleaching purposes, at low temperature and using atmospheric air without any further bleaching agent.

Claims

CLAlMS

1. Method for the catalytic decomposition of peroxides, characterized in that the peroxide is decomposed by means of one or more dioxo-compounds selected from the group of diketones, dialdehydes or ketoaldehydes having a calculated reduction energy (CRE) in the range of from -10 to -30 kcal/mole, the CRE being the energy difference in kcal/mole between the lowest energy conformations of the radical anion and the corresponding neutral molecule as calculated by means of the Turbomole Version 5 program.

2. Method for the catalytic decomposition of peroxides according to claim 1 , wherein the one or more dioxo-compounds each have a CRE between -13 and -17 kcal/ mole.

3. Method for the catalytic decomposition of peroxides according to claim 1 or 2, wherein at least one dioxo-compound of the one or more dioxo-compounds is a vicinal dioxo compound.

4. Method for the catalytic decomposition of peroxides according to claim 3, wherein at least one of the oxo-groups in the vicinal dioxo-compound is a ketone group.

5. Method for the catalytic decomposition of peroxides according to claim 4, wherein the vicinal dioxo-compound is a vicinal diketone.

6. Method for the catalytic decomposition of peroxides according to claims 4 or 5, wherein at least one of the ketone groups in the vicinal dioxo-compound is a methyl ketone.

7. Method for the catalytic decomposition of peroxides according to any of the claims 1 or 6, wherein the peroxide is decomposed by means of one or more dioxo-compounds in combination with a base or a mixture of bases.

8. Method for the catalytic decomposition of peroxides according to claim 7, wherein the base is either an organic or inorganic oxide, hydroxide, alkoxide or carboxylate of which the cation has a redox potential of the metal of at most -1 V, or is an ammonium ion; and/or a nitrogen containing organic compound; or any mixture of such bases.

9. Method for the catalytic decomposition of peroxides according to any of the claims 7 or 8,wherein the cation of at least one of the bases has a redox potential of at most -1 ,5 V.

10. Method for the catalytic decomposition of peroxides according to any of the claims claim 7 to 9, wherein at least one of the bases is an inorganic base.

11. Method for the catalytic decomposition of peroxides according to any of the claims 7 to 10, wherein at least one of the bases is an organo-soluble base.

12. Method for the catalytic decomposition of peroxides according to any of claims 7 to 11 , wherein at least one of the said bases is based on an alkaline or earth alkaline metal, or is an ammonium salt.

13. Method for the catalytic decomposition of peroxides according to claim 12, wherein at least one of the said bases is a Li, Na or K base.

14. Method for the catalytic decomposition of peroxidesaccording to claim 7, wherein at least one of the bases is an amine compound.

15. Method for the catalytic decomposition of peroxides according to any of claims 7 or 14, wherein at least one of the bases is a tertiary amine compound.

16. Method for the catalytic decomposition of peroxides according to any of the claims 1 to 15, wherein the peroxide is a compound from the group of hydrogen peroxide, hydroperoxides and ketone peroxides.

17. Method for the catalytic decomposition of peroxides according to any of claims 1 to 16, wherein the peroxide is a liquid or dissolved peroxide compound.

18. Method for the catalytic decomposition of peroxides according to any of claims 1 to 17, wherein the peroxide is a liquid or dissolved hydroperoxide compound.

19. Method for the catalytic decomposition of peroxides according to any of claims 1 to 18,wherein the decomposition is carried out in a liquid medium.

20. Method for the production of radicals by decomposition of a peroxide according to any of the claims 1 to 19, and use of the radicals formed in an application selected from the group of radical polymerizations, grafting reactions, bleaching, drying of alkyds, epoxidation reactions, sterilization processes, and desinfection processes.