WO2006003032A1

WO2006003032A1 - Silyl polymers

Info

Publication number: WO2006003032A1
Application number: PCT/EP2005/009206
Authority: WO
Inventors: Mark Plehiers; Philippe Ravez
Original assignee: Sigmakalon BV
Current assignee: PPG BV
Priority date: 2004-07-03
Filing date: 2005-07-04
Publication date: 2006-01-12
Anticipated expiration: 2007-01-03
Also published as: TW200619242A

Abstract

A new silatrane side chain containing polymer of (I) is described. Processes for the production of a silatrane polymers of formula I are also described. The polymers have applications as binders such as binders for antifouling coatings.

Description

SILYL POLYMERS

The present invention relates to silyl polymers and also to processes for the production of silyl polymers, in particular, silatrane acrylate polymers. It also relates to the use of such polymers in applications which require hydrolysable binders such as antifouling coatings.

Antifouling paints are widely used to improve the performance of ships by preventing the growth of marine organisms on the sub-marine parts of ship's hulls. Binders containing metals such as tin have been widely used since the 1960's but research has shown that the organotins such as tributyl tin (TBT) cause environmental problems such as deformations in oysters and sex changes in whelks. Finding silyl derived binders as a replacement for such tin-based systems is an important area of research.

Silatranes such as 5-aza-2, 8, 9-trioxa-l- silabicyclo [3.3.3] -undecanes, are cyclic organosilicon ethers of tris (2-oxyalkyl) -amines and their derivatives. Their heterocyclic skeleton may be represented by structure A.

A Silatrane itself, the simplest compound of this class, has structure A where X=H and Rl to R6=H.

Most conventional silatranes contain X= alkyl, aryl, halogen or alkoxy.

Silatrane chemistry and properties are described in some reviews :

M.G.Voronkov, V.M.Dyakov, S .V.Kirpichenko J. of Organometallic Chemistry, 233(1982)1-147; and V.Pestunovich, S .Kirpichenko and M.Voronkov in "The Chemistry of Organic Silicon Compounds", Vol2, p 1447- 1537, Ed Z.Rappoport and Y.Apeloig, 1998, J.Wiley&Sons .

One synthetic route for the preparation of the silatrane skeleton consists in the transesterification of a polyalkoxysilane precursor with the desired trialkanolamine derivative (see Scheme I) .

M.G.Voronkov discloses in Pure and Applied Chemistry, 13,35(1966) a general method for the synthesis of 1- organoxysilatranes based on transesterification of the lower tetraalkoxysilanes by an equimolar mixture of triethanolamine and a corresponding hydroxyl containing compound in the presence of an alkali catalyst (alkali metal hydroxide) .

M.H. P.van Genderen et al. in Recueil des Travaux Chimiques des Pays-Bas, 106(8), 449-52, 1987 also disclose the synthesis of 1-ethoxysilatrane by reaction of tetraethoxysilane with triethanolamine and a catalytic amount of KOH whilst refluxing in xylene. EP0908462, JP1998182669, JP2002097273, EP0919558, EP1002834 and EP1067161 each disclose the synthesis of silatranes by the reaction of amines with epoxies in the presence of a polyalkoxy silane.

US 2,953,545 discloses the synthesis of 1-ethoxy silatrane [3463-21-6] (R7= Et, Rl-R6= H) by the reaction of tetraethylorthosilicate and triethanolamine; US 3,118,921 discloses the synthesis of 1-ethoxy trimethyl silatrane [71229-25-9] (R7=Et; R1,R3,R5= Me; R2, R4, Rβ= H) by the reaction of tetraethylorthosilicate and triisopropanolamine; and US 3,032,576 discloses the synthesis of carbasilatranes by the reaction of gamma aminosilanes with epoxy compounds .

FR2084799, CS128408, HU56019, and ZA6806969 disclose the synthesis of (meth) acryloyloxy containing silatranes of general structure: RCH=CH2CO2 (CH2) nSi (OCHR' CH2) 3N.

US4048206 claims a process for the production of silatranes of the general structure: X-Z-Si (OR) 3N where X is, amongst others, R3CO2.

S.Verma et al . disclose in Indian J.of Chemistry 41B, 608 (2002) the synthesis of various 1- organyltrimethylsilatranes (with Rl, R3, R5=Me;

R2,R4,R6=H) by the reaction of trialkoxysilanes and triisopropanolamine in the presence of catalytic amounts of KOH.

MAc

Vl Scheme I

Only a few syntheses of 1-acyloxy silatranes V or VI are described in the literature:

M.G.Voronkov discloses in Pure and Applied Chemistry, 13,35(1966) the possibility to prepare 1-acyloxysilatranes without any experimental data. It is described that this class of compounds is extremely unstable and their purification a matter of considerable difficulty.

J.Wang et al . in Chemical J.of Chinese Universities 9, 466-469 (1988) discloses the synthesis of 1- acyloxysilatranes by reaction of 1-bromosilatranes with the corresponding carboxylic acid in the presence of pyridine. The disadvantage of this method is the release of bromhydric acid and the formation of K salts. Russian Patent SU 242171 discloses the transformation of 1-hydrosilatrane (Si-H) into the corresponding 1- acyloxysilatrane in the presence of zinc chloride in boiling xylene with a yield of 84%. The disadvantage of this method is the poor accessibility of the starting silane and the release of hydrogen.

C.L.Frye et al describe in J.Am.Chem. Soc 93, 25, 6805 (1971) the transformation of IV (R7= Et, R1-R6=H) into V (R8=Me, R1-R6=H) with a mixture of acetic acid and acetic anhydride at 160°C for 16h.

H.Cheng and R.M.Laine described in New.J.Chem, 1999, 23, 1181-1186 the transformation of IV (R7= CH2CH2OH, R1-R6=H) into V (R8=Me, R1-R6=H) in refluxing acetic anhydride for

12-24h. They also disclosed the transformation of V

(R8=Me, R1-R6=H) into VI (R9= Me, RlO-RIl= H, R1-R6=H) in methacrylic acid as solvent at room temperature for 16 h and evaporation of the solvent under reduced pressure at room temperature. The reaction gives only partial transformation with yields of only 60% or so.

For the purposes of clarity references to R1-R7 in the prior art above should not be equated with references to R1-R7 in the invention hereinafter.

According to a first aspect of the present invention there is provided a polymer P comprising at least one silatrane side group (s) or terminal group of formula I

wherein R¹, R² and R³ each independently represent (CR⁵R⁶I_n- or - (CR⁵R⁶)_mY- , wherein n and m each independently represent a number from 2 to 6 and Y when present is a hetero atom independently selected from 0, N or S;

R⁵ and R each independently represent a hydrogen atom or a halogen, nitro, alkyl, alkenyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from alkyl, alkenyl, alkynyl, alkoxyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro, or each independently represent OR⁷, OC(O)R⁷ or COOR⁷ where R⁷ is selected from alkyl, alkenyl, alkynyl or an aryl radical optionally substituted by one or more groups comprising alkyl, alkenyl, alkynyl, alkoxyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro;

L represents - (CR¹³R¹⁴) _q - wherein R¹³ and R¹⁴ are defined as R⁵ and R⁶ above and q is 0-6; and Z is selected from

Preferably, neither R⁵ or R⁶ are an alkenyloxyalkyl group of formula -R^b-O-R^c, where R^b is an alkylene group and R^c is an alkenyl group. Examples of R^b include methylene, ethylene, methyl methylene and propylene. Examples of R^c include vinyl, allyl, butenyl, pentenyl, and hexenyl, or C₃ to Cio alkenyl groups .

Alternatively, R⁵ and R⁶ each independently represent a hydrogen atom or a halogen, nitro, alkyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from the list given above.

Alternatively, R⁵ and R⁶ each independently represent a halogen, nitro, alkyl, alkenyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from the list given above.

Preferably, polymer P is a copolymer of the type including side chains or terminal groups comprising -ZO- groups such as acrylate polymers etc. Typically, P comprises an acrylic polymer chain, preferably an alkacrylic polymer chain, more preferably, a (meth) acrylate polymer chain. Accordingly, there may be as many side groups of formula I as there are -ZO- containing side chains in the polymer P and therefore, there is no upper limit on the number of such side chains as it will depend on the number of -ZO- groups available on polymer P. Preferably, the Z group attached to a part of the polymer chain is derived from an α-β unsaturated C₃-C₂₀ carboxylic acid monomer or equivalent moiety in a polymer, more preferably, a (Co-₈ alk) acrylic acid monomer or (Co-₈ alk) acrylic acid moiety of the polymer, more preferably, an acrylic acid or methacrylic acid monomer or moiety of the polymer. Preferably, a carbon of the polymer chain is directly attached to the silatrane of formula I at the Z group.

Preferably, the polymer P is not a polydiorganosiloxane polymer, and/or a polymer described by the average unit formula R_aSi0(₄__a)_/2, wherein R represents substituted or unsubstituted monovalent hydrocarbon groups and a is a number between 1.9 and 2.1. Preferably, the polymer P is not a polydiorganosiloxane having at least two alkenyl groups in each molecule.

Preferably, when the polymer P is a polymer wherein Z is attached to a polycyclic and/or norbornene derived moiety of the polymer it is attached to the part of the polycyclic and/or norbornene derived moiety which forms the polymer backbone. More preferably, the polymer P is not a polymer wherein Z is attached to an atom of a polycyclic and/or norbornene derived moiety which itself does not form part of the polymer chain. More preferably, the polymer P is not a polymer wherein Z is attached to a part of the polymer derived from a norbornene-containing moiety. More preferably, the polymer P is not a polymer wherein Z is attached to a part of the polymer derived from a polycyclic monomer.

Preferably, the side chains of formula I are present on 1-

99% of the residual monomer units in the polymer P, more preferably, 5-40%, most preferably, 10-20% of the monomer units . Preferably, alternatively defined, the silatrane of formula I is present in the polymer P in the range 1-99% w/w, more preferably, 5-75% w/w, most preferably 15-55% w/w.

For the avoidance of doubt, preferably more than one side chain of formula I is present on polymer P and in such case each silatrane side chain may be the same or different. Especially preferred is a range of silatranes that include those that are with and without (ie q = 0) a spacer L.

As mentioned above, the polymer P may be a copolymer which may be acrylic based or derived from other suitable monomers. The polymer P can be .a homo or co-polymer

(including terpolymers, etc) having silatrane group (s) of formula I in the side chains or terminal groups.

More generally, the polymers of the present invention may be derived from any known monomer or polymer having acid groups in the side chains or the terminal groups, more preferably, acid groups of formula -Z(OH)_x where X is an integer from 1-3. Preferably, the acid functional monomer is (Co-₈ alk) acrylic acid, more preferably, acrylic acid or methacrylic acid, most preferably, methacrylic acid. Similarly, the acid functional polymer is preferably, derived from a (Co-₈ alk) acrylic acid, more preferably, acrylic acid or methacrylic acid, most preferably, methacrylic acid.

Preferably, non-formula I comonomer unit residues are also present in the polymer P in the range of 5-99% w/w of the total monomer units in polymer P, more preferably, 60-95% w/w, most preferably 80-90% w/w. Preferred comonomers are selected from Ci-Ci₂ alkyl (C₀-C₈ alk) acrylate or (C₀-C₈ alk) acrylic acid, vinyl esters, vinyl amides, vinyl aromatics, polyester or alkyd resin monomers or epoxy monomers . Suitable comonomers are alkacrylic esters such as methyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate; vinyl esters such as vinyl alkanoates, alkenoates, alkynoates or alkarylanoates (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc) ; vinyl amides such as vinyl -NR²³R²⁴, -C(O)NR²⁵R²⁶, amido N containing Het or C(S)NR²⁵R²⁶ wherein R²³ to R²⁶ in such vinyl compounds each independently represent aryl or alkyl (which alkyl group itself may be optionally substituted or terminated as defined below) . Examples include vinyl pyrrolidone, vinyl formamide, etc; vinyl aromatics such as styrene, vinyltoluene, alpha - methylstyrene; polyester or alkyd resins; epoxy resins, or mixtures of any of the foregoing comonomers . Especially preferred comonomer unit residues include ethyl acrylate, butyl acrylate and methyl methacrylate or mixtures thereof.

Although (alk) acrylic, more preferably, (meth) acrylic polymers or copolymers are preferred, the polymer having silatrane side groups may be derived from any monomer/polymer having acid functionality on the side chains thereof such as itaconic, maleic, fumaric, crotonic , sulfonic, phosphonic acids, acid-functional polyester or alkyd resins, acid-modified epoxy resins and the like or copolymers thereof with any of the non-formula I side chain copolymers mentioned above. In the case of the monomers, the polymer of the invention may be obtained from the formula I ester of the relevant -Z(OH)_x monomer.

Especially preferred silatrane comonomer units in the final polymer include (C_O-Q alk) acryloyloxysilatranes, more preferably, methacryloyloxy silatranes or acryloyloxy silatranes, most preferably, methacryloyloxy silatranes.

Preferably, in groups - (CR¹³R¹⁴) _q- , q is 0-3, more preferably 0 or 1.

According to a second aspect of the present invention there is provided a process for the production of silatrane side chain (s) of formula I containing polymers

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹³, R¹⁴, L, and Z are as defined in the first aspect of the invention,

wherein the polymer is produced by one of the following methods :-

(a) polymerisation of the silatrane monomer of formula II

II

wherein R¹, R² and R³ each independently represent

(CR⁵R⁶) _n- or - (CR⁵R⁶)_mY- , wherein n and m each independently represent a number from 2 to 6 and Y when present is a hetero atom independently selected from 0, N or S;

L is defined as in the first aspect of the invention/ R⁵ and R⁶ each independently represent a hydrogen atom or a halogen, nitro, alkyl, alkenyl, alkynyl or aryl radical optionally substituted by one or more groups selected from alkyl, alkenyl, alkynyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro, or each independently represent OR⁷, OC(O)R⁷ or COOR⁷ where R⁷ is selected from alkyl, alkenyl, alkynyl or an aryl radical optionally substituted by one or more groups comprising alkyl, alkenyl, alkynyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro;

R⁸ represents a hydrogen atom, an alkyl group, or (-Rⁿ-)o C(O)OR¹⁰ wherein R¹⁰ represents an alkyl group and wherein R¹¹ is selected from alkyl, alkenyl, alkynyl, aryl or an aralkyl radical, R⁸ and R¹¹ being optionally substituted by one or more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, aryl, hydroxyl, halogen, amino or amino alkyl radicals, and wherein O=O or 1;

R⁹ represents a hydrogen atom, or is selected from an alkyl, aryl, aralkyl, alkenyl or an alkynyl radical optionally substituted with the same radicals as defined for R⁸ above, or R⁹ represents -COOR¹² wherein R¹² represents an alkyl group; or

(b) reaction of a polymer having acid functionality with a reactive silatrane of formula III

III

wherein R¹, R², R³ are as defined above and R⁴ represents a hydrogen radical or an alkyl, alkenyl, alkynyl or aryl radical optionally substituted by one or more groups selected from alkyl, alkenyl, alkynyl, aralkyl, aryl and halogen; or

(c) polymerisation of monomers with acid functionality in the presence of a reactive silatrane of formula III as defined above.

The silatrane polymers obtained according to process (a) of the present invention can be derived from monomers having silatrane groups in the side chains or terminal groups, such as silatrane esters of acrylic, methacrylic, itaconic, male±c, fumaric, crotonic, sulfonic, phosphonic acids and the like, optionally copolymerised with one or more other "neutral" monomers including Ci_₁₀ alkyl (C₀-_S alk) acrylic esters (for example methyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate) , isobutyl (meth) acrylate, etc), C₀-g alk) acrylic acid; butadiene; vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc) , vinyl amides (vinyl pyrrolidone, vinyl formamide, etc) , styrene, vinyltoluene, alpha -methylstyrene) , silatrane-functional polyester or alkyd resins, silatrane- modified epoxy resins, etc.

The silatrane polymers obtained according to process (b) of the present invention can be derived from homo or co¬ polymers (including terpolymers, etc) having acid ZOH groups in the side chains or terminal groups, such as acrylic resins containing unsaturated polymerizable organic acid monomers such as acrylic, methacrylic, itaconic, maleic, fumaric, crotonic, sulfonic, phosphonic acids, acid-functional polyester or alkyd resins, acid- modified epoxy resins, acids and the like, optionally copolymerised with one or more other "neutral" monomers including Ci-Cio alkyl (C₀-Cealk) acrylic esters (for example methyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate) , isobutyl (meth) acrylate, etc); (C₀-C₈ alk) acrylic acid; butadiene vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc) , vinyl amides (vinyl pyrrolidone, vinyl formamide, etc) , styrene, vinyltoluene, alpha -methylstyrene) , polyester or alkyd resins, epoxy resins, etc. The silatrane polymers obtained according to process (c) of the present invention can be derived from monomers having ZOH groups in the side chains or terminal groups, such as acrylic, methacrylic, itaconic, maleic, fumaric, crotonic, sulfonic, phosphonic acids, acid-functional polyester or alkyd resins, acid-modified epoxy resins, and the like, optionally copolymerised with one or more other "neutral" monomers including Cχ-Cio alkyl (Co-Cs alk) acrylic esters (for example methyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate) , isobutyl (meth) acrylate, etc); (Co-Cs alk) acrylic acid, butadiene; vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc) , vinyl amides (vinyl pyrrolidone, vinyl formamide, etc) , styrene, vinyltoluene, alpha -methylstyrene) , polyester or alkyd resins, epoxy resins, etc.

Preferably, the (alk) acrylic silatrane monomer or the acidic functional monomer in processes (a) or (c) comprise respectively 1-95% w/w of total monomer present, more preferably, 5-40% w/w. Preferably, reaction (a) applies to production of polymer of formula I wherein group L has q > 0 in formula -(CR¹³R¹⁴J_q- Preferably, in reactions (b) and (c) q = 0.

Preferably, in reactions (a) and (c) comonomers are present in the range 5-99% w/w of total monomer present, more preferably, 60-95% w/w, most preferably 80-90% w/w.

Preferably, the comonomers are selected from Ci-C₈ alkyl

(C₀-C₈ alk) acrylate or (C₀-C₈alk) acrylic acid, styrene, butadiene. Suitable comonomers are alkacrylic esters such as methyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, ethyl (meth) acrylate) , isobutyl (meth) acrylate; vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc) ; vinyl amides (vinyl pyrrolidone, vinyl formamide, etc) ; styrene, vinyltoluene, alpha -methylstyrene; acid- functional polyester or alkyd resins; acid-modified epoxy resins, etc.

Preferably, in reaction (b) the acidic functional monomer units in the acidic functional polymer comprise 1-95% of the total monomer units, more preferably, 5-40% of the total monomer units, most preferably, 10-20% of the total monomer units in the polymer.

Preferably, in processes (b) and (c) of the invention suitable solvents include non polar inert solvents, cyclic and non-cyclic aliphatic hydrocarbons, aromatic hydrocarbons, cyclic and non cyclic ethers, esters, alcohols and the like, or the produced volatile compound (R4OH) .

Suitable solvents may be independently selected from pentane, cyclopentane, hexane, heptane, cyclohexane, toluene, xylene, benzene, mesitylene, ethylbenzene, octane, decane, decahydronaphthalene, diethyl ether, diisopropyl ether, diisobutyl ether, n-butanol, propyl alcohol, acetic acid and the like or mixtures thereof.

Especially preferred solvents are those, which allow reactive distillation ie. which cause no distillation of any of the reactants but which allow preferential distillation of the produced volatile compound (R4OH) to drive the equilibrium to the right ie. to the production of the silylated polymer. More especially preferred solvents are those which form a low boiling azeotrope with distilled R4OH.

Most preferably, the solvents are independently selected from pentane, hexane, heptane, cyclohexane, toluene and xylene.

Preferably, the processes (b) and (c) include the step of removing formed R⁴OH therefrom either during or after completion of the reaction. Preferably, the R⁴OH is removed by a suitable separation technique such as distillation.

Preferably, n in - (CR⁵R⁶)_n- is 3. Preferably, m in - (CR⁵R⁶)_mY- is 2.

Preferably, Y is 0. When present, Y is preferably linked to the silyl atom in formulas I, II and III.

Preferably, the molar ratio of reactive silatrane to acid groups in either the polymer or monomer at the start of a batch reaction or throughout a continuous reaction (b) or

(c) is in the range 10:1 to 1:10, more preferably, 5:1 to

1:5, most preferably, 2:1 to 1:2. Especially preferred is a ratio which is substantially 1:1.

Preferably, R⁵ and R⁶ are independently a hydrogen radical or independently selected from methyl, ethyl, propyl, iso- propyl, butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, CH₂OR¹⁷, -OC (O)R⁷ or -COOR⁷, more preferably, R⁵ and R⁶ are independently a hydrogen radical, methyl, ethyl or CH₂OR¹⁷, most preferably, a methyl or CH₂OR¹⁷. For the avoidance of doubt, when n or m > 1, each R⁵ or R⁶ group may be the same or different. Preferably, R¹⁷ may be selected form a hydrogen radical, an alkyI₁. aryl, aralkyl or -CH₂CH₂OR¹⁸ group, more preferably, a hydrogen radical, methyl, ethyl or CH₂CH₂OR¹⁸ group, most preferably, a methyl or -CH₂CH₂OR¹⁸ group, wherein R¹⁸ is defined as R¹⁷ above. In the case, wherein R⁵ or R⁶ are CH₂OR¹⁷ and R¹⁷ is -CH₂CH₂OR¹⁸, a - (CH₂CH₂O)_p-R¹⁸ oligomer may form wherein p is between 0-10, more preferably, 0-5, most preferably 0-3. Termination of the said oligomer takes place when R¹⁸ is selected from a hydrogen radical, alkyl, aryl or aralkyl.

In an especially preferred embodiment, R⁵ and R⁶ are independently methyl or 2-ethyloxyl, more preferably R⁵ and R⁶ are independently 2-ethyloxyl .

Preferably, R⁷ is selected from butyl, cresyl, 2- ethyloxyl, neononanoyl including all isomers, more preferably, butyl or 2-ethyloxyl.

Preferably, the halogen is selected from Cl, Br or I, more preferably, Cl or I, most preferably, Cl.

Preferably, R4 is selected from hydrogen, alkyl, R¹⁶C(O)- wherein R¹⁶ represents a hydrogen radical or an alkyl, alkenyl, alkynyl, aryl or alkaryl radical or an aryloxy radical wherein all may be optionally substituted by one or more groups selected from alkyl, alkenyl, alkynyl, aryl, alkaryl or halogen radicals.

Typically, reaction (a), (b) and (c) are carried out in the range 0-200⁰C, more preferably, 60-170⁰C, most preferably, 110- 14O⁰C. Typically, reaction (a) , (b) and (c) are carried out at or near atmospheric pressure although higher and lower pressures are possible.

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

The term "alk" or "alkyl", as used herein unless otherwise defined, relates to saturated hydrocarbon radicals being 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. These radicals may be optionally substituted with a halo, cyano, nitro, OR¹⁹, OC(O)R²⁰, C(O)R²¹, C(O)OR²², NR²³R²⁴, C(O)NR²⁵R²⁶, SR²⁷, C(O)SR²⁷, C(S)NR²⁵R²⁶, aryl or Het, wherein R¹⁹ to R²⁷ each independently represent hydrogen, aryl or alkyl, and/or be interrupted by one or more oxygen or sulphur atoms, or by silano or dialkylsilcon groups. Examples of such radicals may be independently selected from methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, 2-methylbutyl, pentyl, iso-amyl, hexyl, cyclohexyl, 3-methylpentyl, octyl and the like.

The term "alkenyl", as used herein, relates to hydrocarbon radicals having one or several, preferably up to 4, double bonds, being straight, branched, cyclic or polycyclic moieties or combinations thereof and containing from 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, still more preferably 2 to 6 carbon atoms, yet more preferably 2 to 4 carbon atoms. These radicals may be optionally substituted with a hydroxyl, halo, cyano, nitro, OR¹⁹, OC(O)R²⁰, C(O)R²¹, C(O)OR²², NR²³R²⁴, C(O)NR²⁵R²⁶, SR²⁷, C(O)SR²⁷, C(S)NR²⁵R²⁶, aryl or Het, wherein R¹⁹ to R²⁷ each independently represent hydrogen, aryl or alkyl, and/or be interrupted by one or more oxygen or sulphur atoms, or by silano or dialkylsilcon groups. Examples of such radicals may be independently selected from alkenyl groups include vinyl, allyl, isopropenyl, pentenyl, hexenyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, 1-propenyl, 2-butenyl, 2-methyl-2-butenyl, isoprenyl, farnesyl, geranyl, geranylgeranyl and the like.

The term "alkynyl", as used herein, relates to hydrocarbon radicals having one or several, preferably up to 4, triple bonds, being straight, branched, cyclic or polycyclic moieties or combinations thereof and having from 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms, still more preferably from 2 to 6 carbon atoms, yet more preferably 2 to 4 carbon atoms. These radicals may be optionally substituted with a hydroxy,halo, cyano, nitro, OR¹⁹, OC(O)R²⁰, C(O)R²¹, C(O)OR²², NR²³R²⁴, C(O)NR²⁵R²⁶, SR²⁷, C(O)SR²⁷, C(S)NR²⁵R²⁶, aryl or Het, wherein R¹⁹ to R²⁷ each independently represent hydrogen, aryl or lower alkyl, and/or be interrupted by one or more oxygen or sulphur atoms, or by silano or dialkylsilcon groups. Examples of such radicals may be independently selected from alkynyl radicals include ethynyl, propynyl, propargyl, butynyl, pentynyl, hexynyl and the like. 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. These radicals may be optionally substituted with a hydroxy ,halo, cyano, nitro, OR¹⁹, OC(O)R²⁰, C(O)R²¹, C(O)OR²², NR²³R²⁴, C(O)NR²⁵R²⁵, SR²⁷, C(O)SR²⁷, C(S)NR²⁵R²⁶, aryl or Het, wherein R¹⁹ to R²⁷ each independently represent hydrogen, aryl or lower alkyl, and/or be interrupted by one or more oxygen or sulphur atoms, or by silano or dialkylsilcon groups. Examples of such radicals may be independently selected from phenyl, p-tolyl, 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, β-dimethoxy-2- naphthyl, tetrahydronaphthyl, indanyl, biphenyl, phenanthryl, anthryl or acenaphthyl and the like.

The term "aralkyl" as used herein, relates to a group of the formula alkyl-aryl, in which alkyl and aryl have the same meaning as defined above and may be attached to an adjacent radical via the alkyl or aryl part thereof. Examples of such radicals may be independently selected from benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3- (2-naphthyl) -butyl, and the like. The term "Het", when used herein, includes four-to-twelve- membered, preferably four-to-ten-membered ring systems, which rings contain one or more heteroatoms selected from nitrogen, oxygen, sulphur and mixtures thereof, and which rings may contain one or more double bonds or be non- aromatic, partly aromatic or wholly aromatic in character. The ring systems may be monocyclic, bicyclic or fused. Each "Het" group identified herein is optionally substituted by one or more substituents selected from halo, cyano, nitro, oxo, lower alkyl (which alkyl group may itself be optionally substituted or terminated as defined below) OR¹⁹, OC(O)R²⁰, C(O)R²¹, C(O)OR²², NR²³R²⁴, C(O)NR²⁵R²⁶, SR²⁷, C(O)SR²⁷ or C(S)NR²⁵R²⁶ wherein R¹⁹ to R²⁷ each independently represent hydrogen, aryl or lower alkyl (which alkyl group itself may be optionally substituted or terminated as defined below) . The term "Het" thus includes groups such as optionally substituted azetidinyl, pyrrolidinyl, imidazolyl, indolyl, furanyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, triazolyl, oxatriazolyl, thiatriazolyl, pyridazinyl, morpholinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, piperidinyl, pyrazolyl and piperazinyl. Substitution at Het may be at a carbon atom of the Het ring or, where appropriate, at one or more of the heteroatoms .

"Het" groups may also be in the form of an N oxide.

For the avoidance of doubt, the reference to alkyl, alkenyl, alkynyl, aryl or aralkyl in composite groups should be interpreted accordingly, for example the reference to alkyl in aminoalkyl or alk in alkoxyl should be interpreted as alk or alkyl above etc. The term " (alk) acrylate" or " (meth) acrylate" as used herein optionally refers to alkacrylate, methacrylate or the non-alk or non-meth acrylate respectively.

Examples of the silatrane (alk) acrylate monomers of general formula (II) include but are not limited to 1- (meth) acryloyloxysilatrane

1- (meth) acryloyloxy-3, 5, 7-trimethylsilatrane 1- (meth) acryloyloxy-3, 5, 7-triethylsilatrane 1- (meth) acryloyloxy-3, 5, 7-tripropylsilatrane 1- (meth) acryloyloxy-3, 5, 7-tributylsilatrane 1- (meth) acryloyloxy-3, 5, 7-triisobutylsilatrane 1- (meth) acryloyloxy-3, 5, 7-triphenylsilatrane 1- (meth) acryloyloxy-3, 5, 7-tritolylsilatrane 1- (meth) acryloyloxy-3, 5, 7-tricyclohexylsilatrane 1- (meth) acryloyloxy-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane 1- (meth) acryloyloxy-3, 5, 7-tris (hexylmethylene ether) silatrane

1- (meth) acryloyloxy-3, 5, 7-tris (butylmethylene ether) silatrane 1- (meth) acryloyloxy-3, 5, 7-tris (phenylmethylene ether) silatrane

1- (meth) acryloyloxy-3, 5-dimethylsilatrane 1- (meth) acryloyloxy-3, 5-diethylsilatrane 1- (meth) acryloyloxy-3, 5-dipropylsilatrane 1- (meth) acryloyloxy-3, 5-dibutylsilatrane 1- (meth) acryloyloxy-3, 5-diisobutylsilatrane 1- (meth) acryloyloxy-3, 5-diphenylsilatrane 1- (meth) acryloyloxy-3, 5-ditolylsilatrane 1- (meth) acryloyloxy-3, 5-dicyclohexylsilatrane 1- (meth) acryloyloxy-3, 5-di (2-ethylhexylmethylene ether) silatrane

1- (meth) acryloyloxy-3, 5-di (hexylmethylene ether) silatrane 1- (meth) acryloyloxy-3, 5-di (butylmethylene ether) silatrane 1- (meth) acryloyloxy-3, 5-di (phenylmethylene ether) silatrane 1- (meth) acryloyloxy-3-methylsilatrane 1- (meth) acryloyloxy-3-ethylsilatrane 1- (meth) acryloyloxy-3-propylsilatrane 1- (meth) acryloyloxy-3-butylsilatrane 1- (meth) acryloyloxy-3-isobutylsilatrane 1- (meth) acryloyloxy-3-phenylsilatrane 1- (meth) acryloyloxy-3-tolylsilatrane 1- (meth) acryloyloxy-3-cyclohexylsilatrane 1- (meth) acryloyloxy-3- (2-ethylhexylmethylene ether) silatrane

1- (meth) acryloyloxy-3- (hexylmethylene ether) silatrane 1- (meth) acryloyloxy-3- ( butylmethylene ether) silatrane 1- (meth) acryloyloxy-3- (phenylmethylene ether) silatrane 1- (meth) acryloyloxypropylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-trimethylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-triethylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tripropylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tributylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-triisobutylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-triphenylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tritolylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tricyclohexylsilatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tris (hexylmethylene ether) silatrane

1- (meth) acryloyloxypropyl-3, 5, 7-tris (butylmethylene ether) silatrane 1- (meth) acryloyloxypropyl-3, 5, 7-tris (phenylmethylene ether) silatrane

1- (meth) acryloyloxypropyl-3, 5-dimethylsilatrane

1- (meth) acryloyloxypropyl-3, 5-diethylsilatrane 1- (meth) acryloyloxypropyl-3, 5-dipropylsilatrane

1- (meth) acryloyloxypropyl-3, 5-dibutylsilatrane

1- (meth) acryloyloxypropyl-3, 5-diisobutylsilatrane

1- (meth) acryloyloxypropyl-3, 5-diphenylsilatrane

1- (meth) acryloyloxypropyl-3, 5-ditolylsilatrane 1- (meth) acryloyloxy-3, 5-dicyclohexylsilatrane

1- (meth) acryloyloxy-3, 5-di (2-ethylhexylmethylene ether) silatrane

1- (meth) acryloyloxy-3, 5-di (hexylmethylene ether) silatrane

1- (meth) acryloyloxy-3, 5-di (butylmethylene ether) silatrane 1- (meth) acryloyloxy-3, 5-di (phenylmethylene ether) silatrane

1- (meth) acryloyloxypropyl-3-methylsilatrane

1- (meth) acryloyloxypropyl-3-ethylsilatrane

1- (meth) acryloyloxypropyl-3-propylsilatrane

1- (meth) acryloyloxypropyl-3-butylsilatrane 1- (meth) acryloyloxypropyl-3-isobutylsilatrane

1- (meth) acryloyloxypropyl-3-phenylsilatrane

1- (meth) acryloyloxypropyl-3-tolylsilatrane

1- (meth) acryloyloxypropyl-3-cyclohexylsilatrane

1- (meth) acryloyloxypropyl-3- (2-ethylhexylmethylene ether) silatrane

1- (meth) acryloyloxypropyl-3- (hexylmethylene ether) silatrane

1- (meth) acryloyloxypropyl-3- (butylmethylene ether) silatrane 1- (meth) acryloyloxypropyl-3- (phenylmethylene ether) silatrane

1- (meth) acryloyloxymethylsilatrane

1- (meth) acryloyloxymethyl-3, 5, 7-trimethylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-triethylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tripropylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tributylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-triisobutylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-triphenylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tritolylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tricyclohexylsilatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tris (hexylmethylene ether) silatrane

1- (meth) acryloyloxymethyl-3, 5, 7-tris (butylmethylene ether) silatrane 1- (meth) acryloyloxymethyl-3, 5, 7-tris (phenylmethylene ether) silatrane

1- (meth) acryloyloxymethyl-3, 5-dimethylsilatrane 1- (meth) acryloyloxymethyl-3, 5-diethylsilatrane 1- (meth) acryloyloxymethyl-3, 5-dipropylsilatrane 1- (meth) acryloyloxymethyl-3, 5-dibutylsilatrane 1- (meth) acryloyloxymethyl-3, 5-diisobutylsilatrane 1- (meth) acryloyloxymethyl-3, 5-diphenylsilatrane 1- (meth) acryloyloxymethyl-3, 5-ditolylsilatrane 1- (meth) acryloyloxymethyl-3-methylsilatrane 1- (meth) acryloyloxymethyl-3-ethylsilatrane 1- (meth) acryloyloxymethyl-3-propylsilatrane 1- (meth) acryloyloxymethyl-3-butylsilatrane 1- (meth) acryloyloxymethyl-3-isobutylsilatrane 1- (meth) acryloyloxymethyl-3-phenylsilatrane 1- (meth) acryloyloxymethyl-3-tolylsilatrane 1- (meth) acryloyloxymethyl-3-cyclohexylsilatrane

1- (meth) acryloyloxymethyl-3- (2-ethylhexylmethylene ether) silatrane

1- (meth) acryloyloxymethyl-3- (hexylmethylene ether) silatrane

1- (meth) acryloyloxymethyl-3- ( butylmethylene ether) silatrane

1- (meth) acryloyloxymethyl-3- (phenylmethylene ether) silatrane

Suitable reactive silatranes for processes (b) or (c) may be selected from 1-ethoxysilatrane

1-methoxysilatrane

1-propoxysilatrane

1-acetoxysilatrane

1-propionoxysilatrane l-methoxy-3, 5, 7-trimethylsilatrane l-methoxy-3, 5, 7-triethylsilatrane l-methoxy-3, 5, 7-tripropylsilatrane l-methoxy-3, 5, 7-tributylsilatrane l-methoxy-3, 5, 7-triisobutylsilatrane l-methoxy-3, 5, 7-triphenylsilatrane l-methoxy-3, 5, 7-tritolylsilatrane l-methoxy-3, 5, 7-tricyclohexylsilatrane l-methoxy-3, 5, 7-tri (2-ethylhexylmethylene ether) silatrane l-methoxy-3, 5, 7-tri (hexylmethylene ether) silatrane l-methoxy-3, 5, 7-tri (butylmethylene ether) silatrane l-methoxy-3, 5, 7-tri (phenylmethylene ether) silatrane l-methoxy-3, 5-dimethylsilatrane l-methoxy-3, 5-diethylsilatrane l-methoxy-3, 5-dipropylsilatrane l-methoxy-3, 5-dibutylsilatrane l-methoxy-3, 5-diisobutylsilatrane l-methoxy-3, 5-diphenylsilatrane l-methoxy-3, 5-ditolylsilatrane l-methoxy-3, 5-dicyclohexylsilatrane l-methoxy-3, 5-di (2-ethylhexylmethylene ether) silatrane l-methoxy-3, 5-di (hexylmethylene ether) silatrane l-methoxy-3, 5-di (butylmethylene ether) silatrane l-methoxy-3, 5-di (phenylmethylene ether) silatrane l-methoxy-3-methylsilatrane l-methoxy-3-ethylsilatrane l-methoxy-3-propylsilatrane l-methoxy-3-butylsilatrane l-methoxy-3-isobutylsilatrane l-methoxy-3-phenylsilatrane l-methoxy-3-tolylsilatrane

1-methoxy-3-cyclohexylsilatrane l-methoxy-3- (2-ethylhexylmethylene ether) silatrane l-methoxy-3- (hexylmethylene ether) silatrane l-methoxy-3- ( butylmethylene ether) silatrane l-methoxy-3- (phenylmethylene ether) silatrane l-ethoxy-3, 5, 7-trimethylsilatrane l-ethoxy-3, 5, 7-triethylsilatrane l-ethoxy-3, 5, 7-tripropylsilatrane l-ethoxy-3, 5, 7-tributylsilatrane l-ethoxy-3, 5, 7-triisobutylsilatrane l-ethoxy-3, 5, 7-triphenylsilatrane l-ethoxy-3, 5, 7-tritolylsilatrane l-ethoxy-3, 5, 7-tricyclohexylsilatrane l-ethoxy-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane l-ethoxy-3, 5, 7-tris (hexylmethylene ether) silatrane l-ethoxy-3, 5, 7-tris (butylmethylene ether) silatrane l-ethoxy-3, 5, 7-tris (phenylmethylene ether) silatrane l-ethoxy-3, 5-dimethylsilatrane l-ethoxy-3, 5-diethylsilatrane l-ethoxy-3, 5-dipropylsilatrane l-ethoxy-3, 5-dibutylsilatrane l-ethoxy-3, 5-di±sobutylsilatrane l-ethoxy-3, 5-diphenylsilatrane l-ethoxy-3, 5-ditolylsilatrane l-ethoxy-3, 5-dicyclohexylsilatrane l-ethoxy-3, 5-di (2-ethylhexylmethylene ether) silatrane l-ethoxy-3, 5-di (hexylmethylene ether) silatrane l-ethoxy-3, 5-di (butylmethylene ether) silatrane l-ethoxy-3, 5-di (phenylmethylene ether) silatrane l-ethoxy-3-methylsilatrane l-ethoxy-3-ethylsilatrane l-ethoxy-3-propylsilatrane l-ethoxy-3-butylsilatrane

1-ethoxy-3-isobutylsilatrane l-ethoxy-3-phenylsilatrane l-ethoxy-3-tolylsilatrane l-ethoxy-3-cyclohexylsilatrane l-ethoxy-3- (2-ethylhexylmethylene ether) silatrane l-ethoxy-3- (hexylmethylene ether) silatrane l-ethoxy-3- (butylmethylene ether) silatrane l-ethoxy-3- (phenylmethylene ether) silatrane l-propoxy-3, 5, 7-trimethylsilatrane l-propoxy-3, 5, 7-triethylsilatrane l-propoxy-3, 5, 7-tripropylsilatrane l-propoxy-3, 5, 7-tributylsilatrane l-propoxy-3, 5, 7-triisobutylsilatrane l-propoxy-3, 5, 7-triphenylsilatrane l-propoxy-3, 5, 7-tritolylsilatrane l-propoxy-3, 5, 7-tricyclohexylsilatrane l-propoxy-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane l-propoxy-3, 5, 7-tris (hexylmethylene ether) silatrane l-propoxy-3, 5,7-tris (butylmethylene ether) silatrane l-propoxy-3, 5, 7-tris (phenylmethylene ether) silatrane

1 -propoxy-3, 5-dimethylsilatrane l-propoxy-3, 5-diethylsilatrane l-propoxy-3, 5-dipropylsilatrane l-propoxy-3, 5-dibutylsilatrane l-propoxy-3, 5-diisobutylsilatrane l-propoxy-3, 5-diphenylsilatrane l-propoxy-3, 5-ditolylsilatrane l-propoxy-3, 5-dicyclohexylsilatrane l-propoxy-3, 5-di (2-ethylhexylmethylene ether) silatrane l-propoxy-3, 5-di (hexylmethylene ether) silatrane l-propoxy-3, 5-di (butylraethylene ether) silatrane l-propoxy-3, 5-di (phenylmethylene ether) silatrane

1-propoxy -3-methylsilatrane

1-propoxy -3-ethylsilatrane

1-propoxy -3-propylsilatrane 1-propoxy -3-butylsilatrane

1-propoxy -3-isobutylsilatrane

1-propoxy -3-phenylsilatrane

1-propoxy -3-tolylsilatrane

1-propoxy -3-cyclohexylsilatrane l-propoxy-3- (2-ethylhexylmethylene ether) silatrane l-propoxy-3- (hexylmethylene ether) silatrane l-propoxy-3- (butylmethylene ether) silatrane l-propoxy-3- ( phenylmethylene ether) silatrane

1-acetoxy -3,5, 7-trimethylsilatrane 1-acetoxy -3, 5, 7-triethylsilatrane

1-acetoxy -3,5, 7-tripropylsilatrane

1-acetoxy -3,5, 7-tributylsilatrane

1-acetoxy -3,5, 7-triisobutylsilatrane

1-acetoxy -3,5, 7-triphenylsilatrane 1-acetoxy -3, 5, 7-tritolylsilatrane

1-acetoxy -3,5, 7-tricyclohexylsilatrane l-acetoxy-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane l-acetoxy-3, 5, 7-tris (hexylmethylene ether) silatrane l-acetoxy-3, 5, 7-tris (butylmethylene ether) silatrane l-acetoxy-3, 5, 7-tris (phenylmethylene ether) silatrane l-acetoxy-3, 5-dimethylsilatrane l-acetoxy-3, 5-diethylsilatrane l-acetoxy-3, 5-dipropylsilatrane l-acetoxy-3, 5-dibutylsilatrane l-acetoxy-3, 5-diisobutylsilatrane l-acetoxy-3, 5-diphenylsilatrane l-acetoxy-3, 5-ditolylsilatrane l-acetoxy-3, 5-dicyclohexylsilatrane l-acetoxy-3, 5-di (2-ethylhexylmethylene ether) silatrane l-acetoxy-3, 5-di (hexylmethylene ether) silatrane l-acetoxy-3, 5-di (butylmethylene ether) silatrane l-acetoxy-3, 5-di (phenylmethylene ether) silatrane l-acetoxy-3-methylsilatrane l-acetoxy-3-ethylsilatrane

1-acetoxy-3-propylsilatrane

1-acetoxy-3-butylsilatrane l-acetoxy-3-isobutylsilatrane l-acetoxy-3-phenylsilatrane l-acetoxy-3-tolylsilatrane l-acetoxy-3-cyclohexylsilatrane l-acetoxy-3- (2-ethylhexylmethylene ether) silatrane l-acetoxy-3- (hexylmethylene ether) silatrane l-acetoxy-3- (butylmethylene ether) silatrane l-acetoxy-3- (phenylmethylene ether) silatrane

1-propionoxy -3,5, 7-trimethylsilatrane

1-propionoxy -3, 5, 7-triethylsilatrane

1-propionoxy -3,5, 7-tripropylsilatrane 1-propionoxy -3, 5, 7-tributylsilatrane

1-propionoxy -3,5, 7-triisobutylsilatrane

1-propionoxy -3, 5, 7-triphenylsilatrane

1-propionoxy -3, 5, 7-tritolylsilatrane 1-propionoxy -3, 5, 7-tricyclohexylsilatrane l-propionoxy-3, 5, 7-tris (2-ethylhexylmethylene ether) silatrane

1-propionoxy-3, 5, 7-tris (hexylmethylene, ether) silatrane l-propionoxy-3, 5, 7-tris (butylmethylene ether) silatrane l-propionoxy-3, 5, 7-tris (phenylmethylene ether) silatrane l-propionoxy-3, 5-dimethylsilatrane l-propionoxy-3, 5-diethylsilatrane l-propionoxy-3, 5-dipropylsilatrane l-propionoxy-3, 5-dibutylsilatrane l-propionoxy-3, 5-diisobutylsilatrane l-propionoxy-3, 5-diphenylsilatrane l-propionoxy-3, 5-ditolylsilatrane l-propionoxy-3, 5-dicyclohexylsilatrane l-propionoxy-3, 5-di (2-ethylhexylmethylene ether) silatrane l-propionoxy-3, 5-di (hexylmethylene ether) silatrane l-propionoxy-3, 5-di (butylmethylene ether) silatrane l-propionoxy-3, 5-di (phenylmethylene ether) silatrane

1-propionoxy-3-methylsilatrane l-propionoxy-3-ethylsilatrane

1-propionoxy-3-propylsilatrane

1-propionoxy-3-butylsilatrane

1-propionoxy-3-isobutylsilatrane l-propionoxy-3-phenylsilatrane l-propionoxy-3-tolylsilatrane

1-propionoxy-3-cyclohexylsilatrane l-propionoxy-3- (2-ethylhexylmethylene ether) silatrane l-propionoxy-3- (hexylmethylene ether) silatrane l-propionoxy-3- (butylmethylene ether) silatrane l-propionoxy-3- (phenylmethylene ether) silatrane The polymers of the invention may be used in film formation and, particularly, as hydrolysable binders for antifouling coatings.

Accordingly, according to a third aspect of the present invention there is provided a binder for an antifouling coating comprising a polymer in accordance with the first aspect of the present invention.

Still further according to a further aspect of the present invention there is provided the use of a polymer according to the first aspect of the present invention as an hydrolysable binder for an antifouling coating.

Preferably, when R¹, R² or R³ is (CR⁵R⁶)mY-, the silatrane may be conveniently prepared by any of the described methods detailed above in the prior art comprising for example, the reaction of trialkanolamines with tri- or tetraalkoxysilanes and distillation of the released alcohol.

Trialkanolamines may be purchased or obtained by the reaction of the corresponding aminoalcohols and epoxy derivatives such as described in the literature (EP1002834, EP0919558, EP0908462, JP1998182669, JP2002097273) (R.Pozniak and Jchlebicki in Polish J. of Chemistry, 52(6) , 1283-8; 1978 also describes the reaction of aliphatic glycidyl ethers with primary and secondary amines such as ethanolamine or diethanolamine) .

The preparation of the epoxy-amine adducts and its silylation may be done together or in two steps. The present invention also covers any silatrane skeleton that can be suitably obtained from polyalkoxysilanes and trialkanolamine, the latter obtained by the reaction of any beta-aminoalcohol with any monoepoxy derivative. The stoiechiometry relying on the kind of amine used.

Preferably, when R¹, R² or R³ is - (CR⁵R⁶) n-, the silatrane may be conveniently obtained by the reaction of any gamma- aminosilane with two equivalents of monoepoxy derivative such as described in US3, 032,576 or JP2002038014.

The transformation of 1-alkoxy silatranes into the (alk) acrylic monomer may be done by the methods described by Cheng and Laine in New.J.Chem 1999, 23, 1181-1186 or by the new and direct reaction of 1-alkoxysilatranes with (alk) acrylic acid.

Preferably, for use as a binder for antifouling paints, the polymer should have sufficient Mw to be film forming.

Examples :

In the following examples, NMR data have been determined in CDCI₃ (or otherwise stated) and are expressed as delta versus TMS. GC analyses were performed on an Agilent 6890 apparatus equipped with a split injector (split ratio: 1:50, 25O⁰C); a FID detector (280⁰C); a DB-1701 of 15m, 0.32 mm internal diameter and 0.25 micron of film thickness; the elution was performed at a constant pressure of helium and an initial flow of 2.1 ml/min. The compounds were dissolved in acetone, 1 microliter samples were injected at a temperature of 40⁰C, the temperature of the oven was directly risen at a speed of 10°C/min until 250⁰C and maintained at that temperature for 30min. Unless otherwise stated, all the reactants were purchased from Aldrich and were used without purification.

Preparative Example 1: Preparation of l-acetoxy-3, 5, 7- trimethylsilatrane

To 451.0 g of l-ethoxy-3, 5, 7-trimethylsilatrane (CAS nr: 71229-25-9) was added 709.6 g of acetic anhydride. The mixture was heated to 149⁰C while ethyl acetate was continuously distilled out of the reactor.

After cooling, the white precipitate was filtered and the solid dried under vacuum to give 464 g of l-acetoxy-3, 5, 7- trimethylsilatrane (yield: 97%) . This compound is actually a mixture of diastereoisomers (A/B) in a ratiol/3.

¹³C NMR disatereoisomer A: 171.0, 64.7, 64.7, 23.7, 20.3; diastereoisomer B: 171.1, 66.09, 64.4, 63.4, 61.8, 60.5, 59.1, 23.7, 23.4, 20.4, 20.1. GC retention times: 20.5 min (A) and 20.6 min (B)

Preparative Example 2: Preparation of 1-methacryloyloxy- 3,5, 7-trimethylsilatrane

233.8 g of l-acetoxy-3, 5, 7-trimethylsilatrane (prepared as described in Preparative Example 1) and 291.8 g of methacrylic acid were heated at 77⁰C under a pressure of 8 mbar while acetic acid was distilled out of the reactor. The progress of the reaction was monitored by GC. Upon completion, excess of methacrylic acid was distilled off to furnish l-methacryloyloxy-3, 5, 7-trimethylsilatrane as a white solid. This compound is actually a mixture of diastereoisomers (A/B) in a ratiol/3 ¹³C NMR (C6D6) diastereoisomers A+B: 166.7, 166.8, 140.3, 123.9, 66.5, 65.2, 65.0, 64.8, 63.6, 61.8, 61.0, 59.1, 23.6, 20.9, 20.7, 20.5.

GC retention time: 21.12 (A) and 21.29 (b) min

Preparative Example 3 : Preparation of 1-methacryloyloxy- 3, 5, 7-trimethylsilatrane using the direct process. 233.8 g of l-ethoxy-3, 5, 7-trimethylsilatrane (CAS nr: 71229-25-9, 19.78 g of methacrylic acid and 0.1 g of p- methoxyphenol were heated at a temperature ranging from 130 to 142°C while ethanol was distilled out of the reactor. The progress of the reaction was monitored by GC. Upon completion, 100 mL of xylene was added to the reactor and the volatiles were evaporated at a pressure of 8 mbar at a temperature of 65⁰C to furnish 1-methacryloyloxy- 3, 5, 7-trimethylsilatrane as a white solid. This compound has the same characteristics as those described in Preparative Example 2

Preparative Example 4 (acid polymer)

1320 g xylene and 180 g acetic acid__were put in a 4 L 4- necked flask and kept under nitrogen. The four necks of the flask were equipped with stirring means, a reflux cooler, a thermometer for temperature control of the reaction, and means for addition of the monomers.

A premix was prepared in a separate vessel; it contained:

- 167 g of butyl acrylate (BA) [13.9 w% of monomers]

- 832 g of methyl methacrylate (MMA) [69.3 w% of monomers]

- 202 g of methacrylic acid (MAc) [16.8 w% of monomers] - 36 g (= 3% on total monomer weight) of VAZO 67

The premix was added drop by drop to the reaction vessel

(total time: about 4 hours) whilst maintaining the temperature at 100⁰C. Forty-five minutes after the end of the addition of the premix, three post-addition of 2.4 g

(0.2 w%) VAZO67 with 45 minutes interval had been made.

There after the temperature was increased up to 110⁰C for

1 hour to complete the reaction. The solution had been thinned down with 300 g xylene. The binder had a solid content of 43 % and a viscosity of 89 dPa.s This polymer solution contains 76.9 mequiv. methacrylic acid/100g.

Preparative example 5 : Preparation of the l-ethoxy-3- (2- ethylhexylmethylene ether) silatrane. 252.3 g of diethanolamine, 447.1 g of 2-ethylhexylglycidyl ether, 499.9 g of tetraethylorthosilicate and 252.3 g of ethanol were mixed during two hours at room temperature while the temperature of the reactor rose spontaneously to 49°C.The reactor was then heated to 90-99⁰C while ethanol was distilled out of the reactor at atmospheric pressure. When almost all of the ethanol was distilled, the mixture was stripped under vacuum at a temperature of 88⁰C. This gave l-ethoxy-3- (2-ethylhexylmethylene ether) silatrane as a pale brown oil. IR (film) : 2962, 2928, 2874, 1460, 1383, 1276, 1110, 1009, 940, 909, 792 cm^"1. GC retention time: 23.8 min

Preparative example 6: Preparation of the l-acetoxy-3- (2- ethylhexylmethylene ether) silatrane.

203.3 g of the silatrane as prepared in preparative example 4 and 231.3 g of acetic anhydride were heated at a temperature ranging from 130 to 144⁰C while ethyl acetate was distilled out of the reactor. Excess anhydride was then distillated under vacuum. This gave l-acetoxy-3- (2- ethylhexylmethylene ether) silatrane as a pale brown oil. IR (film) : 2961, 2931, 2877, 1740, 1699, 1651, 1459, 1732, 1280, 1238, 1101, 1045, 1013, 970, 809 cm^""1. GC retention time: 22.3 min

Example 1 : Polymerisation of l-methacryloyloxy-3, 5, 7- trimethylsilatrane

151.0 g of xylene was added to a 21 4-necks flask and kept under nitrogen. The four necks of the flask were equipped with stirrings means, a reflux condenser, a thermometer for temperature control of the reaction, and means for addition of the monomers.

A premix was prepared in a separate vessel, containing: -124.0 g of methyl methacrylate -57.2 g of butyl acrylate -45.3 g of l-methacryloyloxy-3, 5, 7-trimethylsilatrane (as prepared in Preparative Example 2 or Preparative Example 3)

-4.53 g (=2% on total monomer weight) 2, 2 ' -azobis (2- methylbutyronitrile (sold under the name Vazo^®67 by DuPont)

The premix was added drop by drop to the reaction vessel (total time = 3 hours) whilst maintaining the temperature at 100⁰C. Thirty minutes after the end of the addition of the premix, five post-additions of 0.1% Vazo^®67 were made at intervals of 45 minutes. 15 minutes after the last post addition, the temperature was increased up to 12O⁰C during one hour. After cooling the binder solution was thinned with 75.5g of xylene to a viscosity of 24 dPa. s and a solids of 39.9%. The binder has a MW of 15000 Da, a drawdown made of the polymer solution on glass yielded a clear dry film. The binder film got a light haze upon 1- day immersion on water. The binder eroded at circa 1 hour at pH 12.3.

Example 2 : Post derivatisation of Preparative Example 3 with of 1-acetoxy, 7-trimethylsilatrane of Preparative Example 1 424.5 g of the acid polymer described in prep. ex. 3, 89.8 g of 1-acetoxy, 7-trimethylsilatrane described in prep. ex.1 and 160 mL xylene had been put into a 1- L 4-necked flask and kept under nitrogen. The four necks of the flask were equipped with stirring means, a thermometer for temperature control, a distillation column with cooler and receiver. The reaction mixture was incompatible until just before the end of the distillation. The mixture had been heated slowly to 140-150⁰C. The yield was 80.3 % on acetic acid after distilling 727 ml. The binder was then diluted with methylethylketone to furnish a final resin with a viscosity of c.a.70 dPa.s and solids of 38.6 %. No residual acetoxy silatrane could be found by GC analysis revealing a total grafting of the silatrane onto the polymer. A drawdown made of the polymer solution on glass yielded a clear dry film The binder film got a light haze upon 1 day immersion in water. The binder eroded in circa 1 hour at pH 12.3.

Example 3 : One Step Procedure with 1-acetoxy, 7- trimethylsilatrane as reactive silatrane 314.4 g of xylene and 54.7 g of 1-acetoxy, 7- trimethylsilatrane described in prep. ex.1 were put in a 4 L 4-necked flask and kept under nitrogen. The four necks of the flask were equipped with stirring means, a reflux cooler, a thermometer for temperature control of the reaction, and means for addition of the monomers.

A premix was prepared in a separate vessel_/ it contained:

- 75 g of butyl acrylate (BA) [13.9 w% of monomers]

- 164.9 g of methyl methacrylate (MMA) [69.3 w% of monomers]

- 17.4 g of methacrylic acid (MAc) [16.8 w% of monomers]

- 7.72 g (= 3% on total monomer weight) of VAZO 67

The premix was added drop by drop to the reaction vessel (total time: about 4 hours) whilst maintaining the temperature at 100⁰C. Forty-five minutes after the end of the addition of the premix, three post-addition of 0.51g (0.2 w%) VAZO67 with 45 minutes interval had been made. Here after the temperature was increased up to 110⁰C for 1 hour to complete the reaction. The four necks of the flask were equipped with stirring means, a thermometer for temperature control, a distillation column with cooler and receiver. 7.62 g of xylene were added and the mixture had been heated slowly to 140-150⁰C whilst a mixture of acetic acid and xylene were distilled off. The yield was 76.1 % on acetic acid after distilling 119 ml. The binder had a solid content of 54.3 % and a viscosity of 41 dPa.s. No residual acetoxy silatrane could be found by GC analysis revealing a total grafting of the silatrane onto the polymer. A drawdown made of the polymer solution on glass yielded a clear dry film The binder film got a light haze upon 1 day immersion in water. The binder eroded in circa 1 hour at pH 12.3. Example 4 : One Step Procedure with l-acetoxy-3- (2- ethylhexylmethylene ether) silatrane as reactive silatrane

294 g of xylene and 70.7 g of l-acetoxy-3- (2- ethylhexylmethylene ether) silatrane described in prep.ex.5 were put in a 4 L 4-necked flask and kept under nitrogen. The four necks of the flask were equipped with stirring means, a reflux cooler, a thermometer for temperature control of the reaction, and means for addition of the monomers.

A premix was prepared in a separate vessel; it contained:

- 56.1 g of butyl acrylate (BA) [23.3 w% of monomers]

- 168.2 g of methyl methacrylate (MMA) [69.9 w% of monomers]

- 16.2 g of methacrylic acid (MAc) [6.75 w% of monomers]

- 7.2 g (= 3% on total monomer weight) of VAZO 67

The premix was added drop by drop to the reaction vessel (total time: about 4 hours) whilst maintaining the temperature at 100⁰C. Forty-five minutes after the end of the addition of the premix, three post-addition of 0.48g (0.2 w%) VAZO67 with 45 minutes interval had been made. Here after the temperature was increased up to HO⁰C for 1 hour to complete the reaction. The four necks of the flask were equipped with stirring means, a thermometer for temperature control, a distillation column with cooler and receiver. 27.8 g of xylene were added and the mixture had been heated slowly to 140-150°C whilst a mixture of acetic acid and xylene were distilled off. The yield was 73 % on acetic acid after distilling 113 ml. The binder had a solid content of 52 % and a viscosity of 79 dPa. s . No residual acetoxy silatrane could be found by GC analysis revealing a total grafting of the silatrane onto the polymer. A drawdown made of the polymer solution on glass yielded a clear dry film. The binder film got a light haze upon 1 day immersion in water. The binder eroded in circa 2 hours at pH 12.3.

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.

Claims

1. A polymer P having at least one silatrane side group (s) or terminal group of formula I

wherein R¹, R² and R³ each independently represent (CR⁵R⁶) _n- or - (CR⁵R⁶)_mY-, wherein n and m each independently represent a number from 2 to 6 and Y when present is a hetero atom independently selected from O, N or S;

R⁵ and R⁶ each independently represent a hydrogen atom or a halogen, nitro, alkyl, alkenyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from alkyl, alkenyl, alkynyl, alkoxyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro, or each independently represent OR⁷, OC(O)R⁷ or COOR⁷ where R⁷ is selected from alkyl, alkenyl, alkynyl or an aryl radical optionally substituted by one or more groups comprising alkyl, alkenyl, alkynyl, alkoxyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro; L represents - (CR¹³R¹⁴) _q - wherein R¹³ and R¹⁴ are defined as

R⁵ and R⁶ above and q is 0-6; and Z is selected from

2. A process for the production of silatrane side chain (s) of formula I containing polymers

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹³, R¹⁴, L, and Z are as defined with respect to the first aspect of the invention,

wherein the polymer is produced by one of the following methods :-

(a) polymerisation of the silatrane monomer of formula II

II

wherein R¹, R² and R³ each independently represent (CR⁵R⁶J_n- or - (CR⁵R⁶)_mY- , wherein n and m each independently represent a number from 2 to 6 and Y when present is a hetero atom independently selected from 0, N or S;

R⁵ and R⁶ each independently represent a hydrogen atom or a halogen, nitro, alkyl, alkenyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from alkyl, alkenyl, alkynyl, alkoxyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro, or each independently represent OR⁷, OC(O)R⁷ or COOR⁷ where R⁷ is selected from alkyl, alkenyl, alkynyl or an aryl radical optionally substituted by one or more groups comprising alkyl, alkenyl, alkynyl, alkoxyl, aralkyl, aryl, halogen, tertiary aminoalkyl or nitro;

L is defined as in the first aspect of the invention; R⁸ represents a hydrogen atom, an alkyl group, or (-R^1:L-)o C(O)OR¹⁰ wherein R¹⁰ represents an alkyl group and wherein R¹¹ is selected from alkyl, alkenyl, alkynyl, aryl or an aralkyl radical, R⁸ and R¹¹ being optionally substituted by one or more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, aryl, hydroxyl, halogen, amino or amino alkyl radicals, and wherein O=O or 1;

(b) reaction of an (alk) acrylic co-polymer having acid functionality with a reactive silatrane of formula III

III

(c) polymerisation of (alk) acrylic monomers comprising at least some (alk) acrylic monomers with acid functionality in the presence of a reactive silatrane of formula III as defined above.

3. A polymer or process according to claim 1 or 2, wherein the silatranes of formula I are present on 1-99% of the monomer units in the polymer P.

4. A polymer or process according to any of claims 1 - 3, wherein R⁵ and R⁶ each independently represent a hydrogen atom or a halogen, nitro, alkyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from the list given above.

5. A polymer or process according to any of claims 1 - 4, wherein R⁵ and R⁶ each independently represent a halogen, nitro, alkyl, alkenyl, alkynyl, alkoxyl or aryl radical optionally substituted by one or more groups selected from the list given above.

6. A polymer or process according to any of claims 1 - 5, wherein the polymer P is a copolymer of the type including side chains comprising Z groups.

7. A polymer or process according to any of claims 1 - 6, wherein the polymer P comprises an acrylic polymer in which the Z group attached to a part of the polymer chain is derived from an α-β unsaturated C₃-C₂0 carboxylic acid monomer or equivalent moiety in a polymer.

8. A polymer or process according to any of claims 1 - 7, wherein the polymer P is not a polydiorganosiloxane polymer, and/or a polymer described by the average unit formula R_aSi0₍₄-_a)/₂, wherein R represents substituted or unsubstituted monovalent hydrocarbon groups and a is a number between 1.9 and 2.1

9. A polymer or process according to any of claims 1 - 8, wherein when Z is attached to a polycyclic and/or norbornene derived moiety of the polymer it is attached to the part of the polycyclic and/or norbornene derived moiety which forms the polymer backbone.

10. A polymer or process according to any of claims 1 - 9, wherein the silatrane of formula I is present in the polymer in the range 1-99% w/w.

11. A polymer or process according to any of claims 1 -

10, wherein the non-formula I side chain comonomer units are present in the range of 5-99% w/w of the total monomer units in polymer P.

12. A polymer or process according to any of claims 1 -

11, wherein the comonomers are selected from Ci-Ci₀ alkyl (Co-Cβ alk) acrylate, (Co-Cg alk) acrylic acid; butadiene; vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc) ; vinyl amides (vinyl pyrrolidone, vinyl formamide, etc) ; styrene, vinyltoluene, alpha -methylstyrene; polyester or alkyd resins; epoxy resins, etc.

13. A polymer or process according to any of claims 1 - 6, 10 or 11, wherein the polymer having silatrane side groups of formula I may be derived from any monomer/polymer having acid functionality on the side chains thereof.

14. A polymer or process according to any of claims 1 to

13. wherein in groups - (CR¹³R¹⁴) _q-, q is 0-3.

15. A polymer or process according to any of claims 1 to 14, wherein n in - (CR⁵R⁶) _n- is 3.

16. A polymer or process according to any of claims 1 to 15, wherein m in - (CR⁵R⁶)_mY- is 2.

17. A polymer or process according to any of claims 1-16, wherein Y is 0.

18. A polymer or process according to any of claims 1-17, wherein Y is linked to the Si atom in formulas I and II.

19. A hydrolysable binder comprising a polymer according to any of claims 1 - 18.

20. A process for the production of a hydrolysable binder comprising the process according to any of claims 1-18.

21. An antifouling coating comprising a polymer according to any of claims 1- 18.

22. A process for the production of an antifouling coating comprising the process according to any of claims 1-18.

23. A polymer or process according to any claims 1-22, wherein the silatrane polymer P comprises residues of one or more of acrylic, methacrylic, itaconic, maleric fumaric, isotonic, sulfonic, phosphonic acids, or acid functional polyester or alkyd resins or acid modified epoxy resins .