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Title:
PROCESS FOR THE PREPARATION OF ACYLOXYSILANES
Document Type and Number:
WIPO Patent Application WO/2004/005302
Kind Code:
A1
Abstract:
Process for the preparation of acyloxysilane comprising the step of reacting, in the presence of a strong acid, a hexahydrocarbyldisiloxane with a carboxylic anhydride.

Inventors:
PLEHIERS MARK (BE)
Application Number:
PCT/EP2003/007103
Publication Date:
January 15, 2004
Filing Date:
July 03, 2003
Export Citation:
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Assignee:
SIGMA COATINGS BV (NL)
PLEHIERS MARK (BE)
International Classes:
C07F7/18; (IPC1-7): C07F7/18
Foreign References:
US2910496A1959-10-27
US4379766A1983-04-12
Other References:
VALADE J: "CHIMIE ORGANIQUE. DERIVES SILICIES. - SCISSION DE MONOSILOXANES SYMETRIQUES", COMPTES RENDUS HEBDOMADAIRES DES SEANCES DE L'ACADEMIE DES SCIENCES, GAUTHIER-VILLARS, PARIS,, FR, vol. 246, 1958, pages 952 - 954, XP009002236, ISSN: 0001-4036
MATSUMOTO H ET AL: "a facile silylation of carboxylic acids with hexamethyldisiloxane", CHEMISTRY LETTERS, CHEMICAL SOCIETY OF JAPAN. TOKYO, JP, 1980, pages 1475 - 1478, XP002181505, ISSN: 0366-7022
Attorney, Agent or Firm:
Walsh, David Patrick (15 Clare Road, Halifax HX1 2HY, GB)
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Claims:
Claims
1. Process for the preparation of acyloxysilanes of either general formula (I) wherein R1 and each R independently represents a hydrogen atom, hydrocarbyl or a substituted hydrocarbyl group or general formula (II) wherein R is as already defined above and R2 represents a bridging hydrocarbyl radical which process comprises the step of reacting, in the presence of a catalyst, a hexahydrocarbyldisiloxane of formula (III) (R) 3SiOSi (R) 3 (111) wherein R is as already defined above either with a carboxylic anhydride of formula (IV) wherein R1 is as already defined above or with a carboxylic anhydride of formula (V) wherein Ruz ils as already defined above with the proviso that there is excluded either a carboxylic anhydride of formula (VI), wherein Rll, R12 each independently represents a hydrogen atom or an alkyl or substituted alkyl group, an aryl or a substituted aryl group, R"represents a hydrogen atom, an alkyl or substituted alkyl group, an aryl or a substituted aryl group orCOOR wherein R6 represents an alkyl, a substituted alkyl, an aryl or a substituted aryl group, or a carboxylic anhydride of formula (VII) wherein R', Rs each independently represents a hydrogen atom or an alkyl or substituted alkyl group, an aryl or substituted aryl group.
2. A process according to claim 1, wherein R each independently represent a linear, branched, or cyclic or polycyclic alkyl, substituted alkyl, aryl or substituted aryl group, saturated or unsaturated, containing from 1 to 12 carbon atoms.
3. A process according to claim 1, wherein R each independently represent a linear, branched, or cyclic or polycyclic alkyl, substituted alkyl, aryl or substituted aryl group, saturated or unsaturated, containing from 1 to 6 carbon atoms.
4. A process according to claim 1, wherein R each independently represent a linear, branched, or cyclic or polycyclic alkyl, substituted alkyl, aryl or substituted aryl group, saturated or unsaturated, containing from 1 to 4 carbon atoms.
5. A process according to claim 1, wherein R is chosen from the group consisting of methyl, ethyl, npropyl, isopropyl, nbutyl, ibutyl, secbutyl, tbutyl, 2 methylbutyl, 2,3dimethylbutyl, lauryl, pentyl, n amyl, isoamyl, nhexyl, cyclohexyl, 3methylpentyl, noctyl, toctyl, ndodecyl, phenyl or substituted phenyl, and the like.
6. A process according to claim 5 wherein R each independently are chosen from the group of methyl, ethyl, npropyl, isopropyl, nbutyl, ibutyl, t butyl, phenyl or substituted phenyl.
7. A process according to claim 6 wherein R are nbutyl or isopropyl.
8. A process according to claims 1 to 7, wherein the carboxylic anhydrides are selected from the group of formic anhydride, acetic anhydride, propionic anhydride, butyric anhydride succinic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, 3 methyl glutaric anhydride.
9. A process according to any preceding claim, wherein the strong acid has a pka value less than2.5.
10. A process according to any preceding claims, wherein the catalyst is independently selected from sulfuric acid, phosphoric acid, chlorhydric acid, bromhydric acid, hydriodic acid, nitric acid, trifluoromethanesulfonic acid or perfluoroalkylsulfonic acids, methanesulfonic acid, paratoluene sulfonic acid or trifluoroacetic acid.
11. A process according to any of claims 110 wherein the catalyst is a strong ion exchange resin effective to catalyse the process of the invention.
12. A trihydrocarbylsilylated carboxylate as defined in formula I or formula II produced by a process in accordance with any one of claims 111.
Description:
Process for the preparation of acyloxysilanes Field of the invention The invention relates to a new method for the preparation of acyloxysilanes.

Background Acyloxysilanes are valuable intermediates in organic synthesis. Indeed they are considered as highly reactive coupling and silylating agents. Several processes are known for the synthesis of acyloxysilanes.

T. W. Greene and P. G. M. Wuts disclose in"Protective groups in organic synthesis" (J. Wiley & Sons, Inc., <BR> <BR> New York, 3rd. ed. , 1999) the synthesis of acyloxysilane from carboxylic acid and silicon halide in the presence of a base.

The reaction of silyl hydrides with carboxylic acids in the presence of various metal catalysts to provide acyloxysilanes is dislosed in Zh. Obshch. Khim. 24,861, 1954, Bull. Chem. Soc. Jap. 62 (2), 211,1989 and in Org.

Letters 2 (8), 1027,2000. These methods have the disadvantage of releasing hydrogen as by product.

US 4,379, 766 discloses the reaction of a carboxylic acid salt with a silicon halide in the presence of phase transfer catalysts to produce acyloxysilane. This reaction has the disadvantage to yield as by-product a halide salt, which has to be removed by filtration.

J. Valade describes in"C. R. Acad. Sci."n° 246, pp. 952-953 (1958) the reaction at reflux of hexamethyldisiloxane or hexaethyldisiloxane with acetic

anhydride or benzoic anhydride in the presence of zinc chloride whereas hexaphenyldisiloxane does not react with acetic anhydride or benzoic anhydride in the presence of zinc chloride.

The object of the present invention is to provide an advantageous process to produce acyloxysilanes.

Another object of the present invention is to provide an advantageous process allowing to produce alkyl substitued acyloxysilanes other than known trimethylacyloxysilanes and triethylacyloxysilanes.

Yet another object of the present invention is to produce acyloxysilanes without any by-product offering an improvement vis-a-vis the disadvantage disclosed above.

The present inventor has surprisingly found that by reacting hexahydrocarbyldisiloxane with saturated carboxylic anhydride in the presence of a strong acid catalyst, acyloxysilane could be synthesised.

The present invention provides a novel process capable of readily preparing acyloxysilanes in a high yield from easily available starting materials.

Summary of the invention The present invention relates to a new process for the preparation of acyloxysilanes of either general formula (I)

wherein R1 and each R independently represents a hydrogen atom, hydrocarbyl or a substituted hydrocarbyl group or general formula (II)

wherein R is as already defined above and R2 represents a bridging hydrocarbyl radical which process comprises the step of reacting, in the presence of a catalyst, a hexahydrocarbyldisiloxane of formula (III) (R) 3Si-O-Si (R) 3 (III) wherein R is as already defined above either with a carboxylic anhydride of formula (IV) wherein R1 is as already defined above or with a carboxylic anhydride of formula (V)

wherein R2 is as already defined above with the proviso that there is excluded either a carboxylic anhydride of formula (VI), wherein R", R"each independently represents a hydrogen atom or an alkyl or substituted alkyl group, an aryl or a substituted aryl group, R"represents a hydrogen atom, an alkyl or substituted alkyl group, an aryl or a substituted aryl group or-COOR'wherein R'represents an alkyl, a substituted alkyl, an aryl or a substituted aryl group, or a carboxylic anhydride of formula (VII) wherein R4, Rs each independently represents a hydrogen atom or an alkyl or substituted alkyl group, an aryl or substituted aryl group.

The catalyst used in the present invention preferably, consists of a strong acid.

The term hydrocarbyl or substituted hydrocarbyl as used herein preferably represents an alkyl, substituted alkyl, an aryl group or substituted aryl group respectively.

The term"alkyl", as used herein unless otherwise defined,. relates to saturated hydrocarbon radicals having straight, branched, cyclic or polycyclic moieties or combinations thereof and contains 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, yet more preferably 1 to 4 carbon atoms. Said radical may be a substituted alkyl group, i. e. optionally substituted with one or more substituents independently selected from alkyl, aryl, alkoxy, halogen, hydroxy or amino radicals.

Examples of such alkyl radicals may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, 2,3- dimethylbutyl, lauryl, pentyl, iso-amyl, n-amyl, n-hexyl, cyclohexyl, 3-methylpentyl, n-octyl, t-octyl, n-dodecyl and the like.

In a preferred embodiment R, Ru, R, R3, R4, R5, R", R and R13 each independently represent a linear, branched, or cyclic or polycyclic alkyl, substituted alkyl, aryl or

substituted aryl group, saturated or unsaturated, containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, yet more preferably R is 4 carbon atoms. Preferably, R is chosen from the group consisting of methyl, ethyl, n- propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-methylbutyl, 2, 3-dimethylbutyl, lauryl, pentyl, n-amyl, iso-amyl, n-hexyl, cyclohexyl, 3-methylpentyl, n-octyl, t- octyl, n-dodecyl, phenyl or substituted phenyl, and the like. More preferably, R is chosen from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2,3-dimethylbutyl, n-amyl, n- hexyl, n-octyl, t-octyl, n-dodecyl, lauryl, phenyl or substituted phenyl wherein the substituents may be linear or branched alkyl, aryl, halogene, alkoxy, phenoxy or nitro. Yet in a more preferred embodiment R is n-butyl, or isopropyl.

In a preferred embodiment Ru, R2, R3, R4, R5, R1l, R12 and R13 each independently represent hydrogen atom or a methyl, n- butyl or isopropyl group.

The term"aryl"as used herein, relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic. Said radical may be a substituted aryl group ie optionally substituted with one or more substituents independently selected from alkyl, alkoxy, halogen, hydroxy or amino radicals.

Examples of aryl includes phenyl, p-methylphenyl, stearyl, phenethyl, (2-methyl)-phenethyl, 4-methoxyphenyl, 4- (tert- butoxy) phenyl, 3-methyl-4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 3-aminophenyl, 3- acetamidophenyl, 4-acetamidophenyl, 2-methyl-3- acetamidophenyl, 2-methyl-3-aminophenyl, 3-methyl-4-

aminophenyl, 2-amino-3-methylphenyl, 2,4-dimethyl-3- aminophenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1- naphthyl, 2-naphthyl, 3-amino-l-naphthyl, 2-methyl-3- amino-1-naphthyl, 6-amino-2-naphthyl, 4,6-dimethoxy-2- naphthyl, tetrahydronaphthyl, indanyl, biphenyl, phenanthryl, anthryl or acenaphthyl and the like.

As used herein, the term"independently"indicates that each radical so described, can be identical or different.

In a preferred embodiment R each independently represent a linear, branched or cyclic alkyl group. An alkyl group as referred to herein may be substituted or unsubstituted or unsaturated and preferably, contain from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, yet more preferably 4 carbon atoms. More preferably, R is chosen from the group of methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl. In a more preferred embodiment R is n- butyl or isopropyl.

Detailed description of the invention The present invention relates to a new process for the synthesis of acyloxysilanes according either to the general scheme : 0 R1q0 catalyst 0 (R) 3Si-O-Si (R) 3 + O-- 2 R1--" R1- 0-S) (R) 3 0 (111) (IV) (I) or to the general scheme: catalyst p O (R) 3Si-O-Si (R) 3 + (2) (R2).--l (R) 3Si-O O-Si (R) 3 0 (III) (V) Carboxylic anhydride represented by the above formula (IV) or (V) is mixed with hexahydrocarbyldisiloxane of formula (III) optionally in the presence of an inert solvent.

The reaction may be conducted under atmospheric pressure and can take place at a temperature within the range of from 25°C to 140°C, preferably from 25°C to 100°C, more preferably from 25°C to 90°C. The conditions of reaction (temperature and time of reaction) may be chosen such as to get the desirable reaction yield.

The reaction progress may be monitored by any suitable analytical method.

Examples of carboxylic anhydrides, which can be used in the process according to the invention, include formic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, tetrahydrophthalic anhydride and 3-methyl glutaric anhydride.

Examples of solvents, which can be used in the process according to the invention, include hexane, cyclohexane, toluene, xylene, pentane, heptane, benzene, mesitylene, ethylbenzene, octane, decane, decahydronaphthalene, diethylether, diisopropyl ether, diisobutyl ether, THF,

Dioxane, dichloromethane or mixtures thereof. Preferably, an inert solvent is used, more preferably, a hydrocarbon inert solvent such as hexane, toluene or xylene.

The reaction progress may be monitored by any suitable analytical method.

The reaction may be without solvent and accordingly suitable ranges of solvent are 0-99 wt% of the total reaction mix, more preferably, 0-80 wt%, most preferably 0-70 wt%.

Examples of acyloxysilanes prepared by the process of the invention using acetic anhydride include trimethylsilyl acetate, triethylsilyl acetate, tri-n-propylsilyl acetate, triisopropylsilyl acetate, tri-n-butylsilyl acetate, triisobutylsilyl acetate, tri-s-butylsilyl acetate, tri-n- amylsilyl acetate, tri-n-hexylsilyl acetate, tri-n- octylsilyl acetate, tri-n-dodecylsilyl acetate, triphenylsilyl acetate, tri-p-methylphenylsilyl acetate, tribenzylsilyl acetate, tri t-butylsilyl acetate. Other examples include ethyldimethylsilyl acetate, n- butyldimethylsilyl acetate, t-butyl dimethylsilyl acetate diisopropyl-n-butylsilyl acetate, n-octyldi-n-butylsilyl acetate, diisopropylstearylsilyl acetate, dicyclohexylphenylsilyl acetate, t-butyldiphenylsilyl acetate, phenyldimethylsilyl acetate and lauryldiphenylsilyl acetate.

Examples of acyloxysilanes prepared by the process of the invention using succinic anhydride include hexamethylsilyl succinate, hexaethylsilyl succinate, hexa-n-propylsilyl succinate, hexaisopropylsilyl succinate, hexa-n-butylsilyl succinate, hexaisobutylsilyl succinate, hexa-s-butylsilyl succinate, hexa-n-amylsilyl succinate, hexa-n-hexylsilyl succinate, hexa-n-octylsilyl succinate, hexa-n-

dodecylsilyl succinate, hexaphenylsilyl succinate, hexa-p- methylphenylsilyl succinate, hexabenzylsilyl succinate, hexa t-butylsilyl succinate. Other examples include bis (ethyldimethylsilyl) succinate, bis (n- butyldimethylsilyl) succinate, bis (t-butyl dimethylsilyl) succinate, bis (diisopropyl-n-butylsilyl) succinate, bis (n-octyldi-n-butylsilyl) succinate, bis (diisopropylstearylsilyl) succinate, bis (dicyclohexylphenylsilyl) succinate, bis (t- butyldiphenylsilyl) succinate, bis (phenyldimethylsilyl) succinate and bis (lauryldiphenylsilyl) succinate.

Examples of acyloxysilanes prepared by the process of the invention using glutaric anhydride include hexamethylsilyl glutarate, hexaethylsilyl glutarate, hexa-n- propylsilylglutarate, hexaisopropylsilylglutarate, hexa-n- butylsilyl glutarate, hexaisobutylsilyl glutarate, hexa-s- butylsilyl glutarate, hexa-n-amylsilyl glutarate, hexa-n- hexylsilyl glutarate, hexa-n-octylsilyl glutarate, hexa-n- dodecylsilyl glutarate, hexaphenylsilyl glutarate, hexa-p- methylphenylsilyl glutarate, hexabenzylsilyl glutarate, hexa t-butylsilyl glutarate. Other examples include bis (ethyldimethylsilyl) glutarate, bis (n- butyldimethylsilyl) glutarate, bis (t-butyl dimethylsilyl) glutarate, bis (diisopropyl-n-butylsilyl) glutarate, bis (n-octyldi-n-butylsilyl) glutarate, bis (diisopropylstearylsilyl) glutarate, bis (dicyclohexylphenylsilyl) glutarate, bis (t- butyldiphenylsilyl) glutarate, bis (phenyldimethylsilyl) glutarate and bis (lauryldiphenylsilyl) glutarate.

The reaction is conducted in the presence of a catalyst, preferably a catalyst consisting of a strong acid. By

"strong acid'', we mean an acid having a pKa value preferably less than 5, more preferably less than-2.5, and most preferably less than-5. Preferably, the "strong acid''is stronger than acetic acid, more preferably stronger than chloroacetic acid, most preferably, stronger than sulphuric acid. Among strong acids that can be used, one can independently select from sulfuric acid, phosphoric acid, chlorhydric acid, bromhydric acid, iodhydric acid, trifluoromethanesulfonic acid or perfluoroalkylsulfonic acids, methanesulfonic acid, para-toluene sulfonic acid, trifluoroacetic acid.

Strong ion exchange resins (sulfonated styrene copolymers) such as Amberlyst@ 15 resin (CAS RN = 39389-20-3) or perfluoroalkylsulfonic resins such as NafionO NR50 resin (CAS RN = 118473-68-0) may also be used.

Preferably, the strong acid catalyst is present at a level of 0.2-40 mol % (mol/mol siloxane), more preferably 1-24 mol %, most preferably 2-10 mol % in the reaction medium at the start of the reaction. In a batch process, the catalyst level relative to moles of siloxane in the starting reaction medium will increase during the reaction, whereas in a continuous process the catalyst level will remain relatively constant throughout the process except towards the end of any such process when it may rise relative to the level of siloxane as feed reactants are no longer added to the process.

The reaction is preferably carried out at a temperature between 0°C and 130°C, more preferably between 10°C and 120°C, and most preferably between 20°C and 100°C, for example at room temperature or 50°C.

Preferably, the reaction takes place in less than 72 hours, more preferably, less than 60 hours, most preferably less than 50 hours.

Preferably, the molar ratio of siloxane: anhydride is between 1: 100 and 50: 1, more preferably between 10: 1 and 1: 10, most preferably, between 2: 1 and 1: 2. Preferably, the molar ratio of siloxane: anhydride is approximately 1: 1.

The reaction may be carried out at any convenient pressure, for instance atmospheric pressure.

The advantage of this invention is that the process uses reactants that can be easily handled. Indeed, hexahydrocarbyldisiloxanes may be considered as easily accessible since they are formed as by-product during acidic deprotection of silyl protected reactive functional groups such as e. g. alcohols, amines or carboxylic acids (as described in"Protective Groups in Organic Synthesis" T. W. Greene and P. G. M. Wuts, J. Wiley & Sons, 1999).

Another advantage lies in the simplicity of the procedure (no by-products).

Indeed even if the reaction is not completed (yield of reaction less than 100%), there are no by-products formed.

Only hexahydrocarbyldisiloxane and carboxylic anhydride that have not reacted remain. Those can be distilled in order to get pure acyloxisilane.

Examples and comparative examples All the reactants used in the examples and comparative examples were purchased from Aldrich and used without any preliminary purification.

NMR datas have been determined in CDC13 and are expressed as delta versus TMS.

Examples 1 to 4 have been conducted according to the invention.

Comparative examples 1 to 3 have been conducted according to J. Valade in C. R. Acad. Sci. n° 246, pp. 952-953 (1958).

Example 1 44.08 g of hexamethyldisiloxane, 28.4 g of acetic anhydride and 2.3 g of trifluoromethanesulfonic acid were stirred at room temperature for 48 hours to furnish trimethylsilyl acetate. The yield of the reaction was 78%.

Trimethysilyl acetate : 13C NMR: 172.0, 22.9, 0.1 ; 25Si NMR: 23.1 ; IR (film): 2962,1724, 1372,1256, 1054,1020, 938, 852 cm~1.

Example 2 44.08 g of hexamethyldisiloxane, 28.4 g of acetic anhydride and 52.3 g of dry Amberlyst A15 (ion exchange resin) were stirred at 50°C for 6 h to furnish trimethylsilyl acetate. The yield of the reaction was 91%.

Trimethysilyl acetate : 13C NMR: 172.0, 22.9, 0.1 ; 29Si NMR: 23.1 ; IR (film): 2962,1724, 1372,1256, 1054,1020, 938, 852 cm~1.

Example 3 8.76 g of hexabutyldisiloxane, 2.16 g of acetic anhydride and 0.16 g of trifluoromethane sulfonic acid were stirred at room temperature for 48 h to furnish tributylsilyl acetate. The yield of the reaction was 67%.

Tributysilyl acetate: 13C NMR: 172.2, 26.7, 25.4, 22.9, 14.1, 13.5 ; 25Si NMR: 22.6 ; IR (film): 2959,2927, 1726, 1371,1257, 1083,1019, 934,887 cm~1.

Example 4 11.8 g of hexamethyldisiloxane, 5 g of glutaric anhydride and 0.98 g of trifluoromethane sulfonic acid were stirred in toluene at 90°C for 24 h to furnish hexamethyldisilyl glutarate. The yield of the reaction was 75%.

Hexamethyldisilyl glutarate : 13C NMR: 173.7, 34.8, 20.3,- 0.1 ; 29Si NMR: 23.23 ; IR (film): 2964,1717, 1377,1256, 1210,1028, 852 cm 1.

Comparative Example 1 5g of hexamethyldisiloxane, 3.1 g of acetic anhydride and 0.8 g of dry zinc chloride were stirred at 110°C for 2 h to furnish trimethylsilyl acetate. The yield of the reaction was 67%.

Trimethysilyl acetate : 13C NMR: 172.0, 22.9, 0.1 ; 29Si NMR: 23.1 ; IR (film): 2962,1724, 1372,1256, 1054,1020, 938, 852 cm~1.

Comparative Example 2 5g of hexamethyldisiloxane, 3.1 g of acetic anhydride and 0.8 g of dry zinc chloride were stirred at room temperature for 24 hours to furnish trimethylsilyl acetate. After 24 hours, no transformation was observed.

Comparative Example 3 5g of hexabutyldisiloxane, 2.16 g of acetic anhydride and 0.32 g of dry zinc chloride were stirred at 110°C. After 24 hours, no transformation was observed.

Comparative Example 4

5g of hexa-isopropyldisiloxane, 1.56 g of acetic anhydride and 0.32 g of dry zinc chloride were stirred at 110°C.

After 24 hours, no transformation was observed.

The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.

All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.

Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

The invention is not restricted to the details of the foregoing embodiment (s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.