Title of Invention	NOVEL ALKOXYAMINES CONTAINING UNSATURATED GROUPS
Abstract	The invention relates to new alkoxyamines suitable for hydrosilylation reactions, to siloxane modified alkoxamines and to siloxane modified polymers and to their use as slip and leveling agent or as dispersant. The alkoxamines are compounds of formula (I) or (II) wherein A is a group capable of forming a stable free nitroxyl radical A, which is bound via its oxygen atom to the carbon atom; R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyl or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(CrC4alkyl)amino; R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyI or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring; R6 is hydrogen or C1-C18alkyI or phenyl; X is O, NH or NR7, wherein R7 is C1-C18alkyI, C3-C8cycloalkyI or phenyl; Y is a direct bond, C1-C30alkylene or C6-C12arylene, with the proviso that the compound of formula I is not

Title of Invention

NOVEL ALKOXYAMINES CONTAINING UNSATURATED GROUPS

Abstract

The invention relates to new alkoxyamines suitable for hydrosilylation reactions, to siloxane modified alkoxamines and to siloxane modified polymers and to their use as slip and leveling agent or as dispersant. The alkoxamines are compounds of formula (I) or (II) wherein A is a group capable of forming a stable free nitroxyl radical A, which is bound via its oxygen atom to the carbon atom; R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyl or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(CrC4alkyl)amino; R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyI or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring; R6 is hydrogen or C1-C18alkyI or phenyl; X is O, NH or NR7, wherein R7 is C1-C18alkyI, C3-C8cycloalkyI or phenyl; Y is a direct bond, C1-C30alkylene or C6-C12arylene, with the proviso that the compound of formula I is not

Full Text	Novel Alkoxyamines Containing Unsaturated Groups The invention relates to new alkoxyamines suitable for hydrosilylation reactions, to siloxane modified alkoxamines and to siloxane modified polymers as well as to their use. The International Publication WO2004/029156 (Ciba) describes a process for the preparation of a triblock-copolymer or graft-copolymer via controlled free radical polymerization using NOR functional polysiloxanes. A polysiloxane is reacted with an ethylenically unsaturated functional alkoxyamine of formula (!) (I) under hydrosilylation conditions. Polymers containing e.g, poly-styrol- polysiloxane-poly-styrol blocks are obtained. Chem. Commun., 2004, 174-175 describes radical cyclization reactions using alkoxyamines as starting material. The alkoxamines disclosed therein are disclaimed. It has been found that using specific alkoxyamines as hydrosilylation agent, siloxane modified alkoxamines having an improved activity in polymerising acrylates can be obtained. One aspect of the invention is a compound of formula (I) or (II) wherein A is a group capable of forming a stable free nitroxyl radical A. which is bound via its oxygen atom to the carbon atom; R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyI or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; R3, R4 and R5 independently of one another are hydrogen or C1-C4alkyl or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring; R6 is hydrogen or C1-C18alkyl or phenyl; X is O, NH or NR7, wherein R7 is C1-C18alkyl, C3-C8cycloalkyl or phenyl; Y is a direct bond, C1-C30alkylene or C6-C12arylene, with the proviso that the compound of formula I is not wherein A, R1, R2, R3, R4, R5. R6. X and Y independently of one another are as defined above under formula (I) or (II) and a is 1 or 2, or a whole number between 1 and 100, W is a linear or branched monofunctional, difunctional or multifunctional polysiloxane residue. Furthermore the invention relates to a siloxane modified polymer or copolymer which is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (I) or (II) as defined above under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la), (lla)or(llb) b) reacting the resulting alkoxyamine functional polysiloxane (la), (lla) or (lib) with at least one vinylic monomer at a temperature between 60 and 160° C. Furthermore the invention relates to the use of a siloxane modified polymer or copolymer which is obtained as described above as slip and leveling agent or as dispersant. Furthermore the invention relates to the use of a siloxane modified polymer or copolymer as slip and leveling agent or as dispersant, whereby the polymer or copolymer is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (III), (IV), (V) or (VI) under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (IlIa), (IVa or IVb), (Va), (Via or VIb) wherein A, R1, R2, R3, R4, R5, R6. X and Y, W, a are as defined above under formula (I) c) reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic nnonomer at a temperature between 60 and 160°C. Preferences: Preferred is a compound of the formula I and a siloxane modified initiator of the formula la and a siloxane modified polymer or copolymer which is obtained by d) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (I) under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la), e) reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer at a temperature between 60 and 160°C. Vinylic monomers The vinylic monomer is selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic acid (C1-C22)alkyl esters, acrylic acid (C1-C22)-hydroxyalkyl esters, methacrylic acid (C1-C22)alkyl esters, methacrylic acid (C1-C22)hydroxy-alkyl esters, acrylic acid (C1-C22)alkyl esters or methacrylic acid (C1-C22)alkyl esters which are substituted by amino, (C1-C22)alkylamino, (C1-C22)dialkylamino, -SO3H, epoxy. fluoro, perfluoro or siloxane groups, styrene, substituted styrene, acrylamide and methacrylamide. N-mono(C1-C22)alkyl acrylamide, N,N-di(C1-C22)alkyl acrylamide; provided that the amount of unsubstituted acrylic acid (C1-C22)alkyl esters or/and methacrylic acid (C1-C22)alkyl esters is more than 30 % by weight based on the weight of the total monomer mixture. Preferably the vinylic monomer Is styrene, methylacrylate, ethylacrylate, n-butylacrylate, iso-butylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethyl-aminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)-acryiate, hydroxyethyl(meth)acrylate. hydroxypropyl(meth)acrylate, dimethylaminoethyi-(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide. methacryiamide or dimethylaminopropyl-methacrylamide or mixtures of them. In a preferred embodiment the vinylic monomer is an acrylic monomer. If the siloxane modified polymer is used as slip and leveling agent the especially preferred vinylic monomer is selected from methylacrylate, ethylacrylate, ethylhexylacrylate, propyl-acrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate, styrene, vinylpyridine. If the siloxane modified polymer is used as dispersant the especially preferred vinylic monomer is an acrylic acid (C1-C22)alkyl esters or methacrylic acid (C1-C22)alkyl esters which are substituted by amino, (C1-C22)alkylamino, (C1-C22)dialkylamino, e.g. dimethylaminoethyl-(meth)acrylate. In the context of this invention, the term "polymer" refers to a polymer of any type including homopolymers and copolymers. The term "copolymer" is meant to include polymers containing groups or units derived from two or more monomers with random, diblock, and multi-block microstructures. The copolymer can be block(co)polymers, comb(co)polymers, star(co)polymers, dendritic(co)polymers or hyperbranched(co)polymers. Block structures such as diblock, triblock are preferred. In other words, after completing the polymerization of a first monomer to the extent desired to form a first polymer "block", a second monomer is introduced into the reaction mass to effect polymerization of the second monomer to form a second polymer "block" that is attached to the end of the first block. Using this sequential addition process, a broad range of diblock, triblock, etc. copolymers can be prepared. The term "copolymer" also includes gradient copolymers or tapered copolymers which are copolymers composed for example of two monomers or monomer mixtures A and B in whose individual chains there is a gradient in the distribution of the monomer units along the chains. One end of the chain is rich in A units and the other in B units. Such copolymers show a continuous transition of one monomer or monomer mixture A into another monomer of monomer mixture B along the polymer chain. Polysiloxanes The Si-H functionalized polysiloxane is linear or branched and is commercially available or can be produced via known methods (Silicone, Chemie und Technologie [Silicones. Chemistry and Technology], Vulkan Publishers, Essen 1989, pp 82-84). The Si-H functionalized polysiloxanes contains at least one unit corresponding to the general formula H(R2)2SiOi/2 wherein R is C1-C6alkyl or phenyl, preferably methyl. The Si-H unit or Si-H units can be in alpha and/or omega position or can be distributed. Thus, the siloxanes are taken from the group consisting of linear siloxanes. comb-like siloxanes , T-branched siloxanes. Definitions: C1-C28alkyl radicals are linear or branclied and are, for example, methyl, ethyl and the various position isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl. dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl. C3-C8cycloalkyl is. for example, cyclopropyl. dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. C1-C30alkylene bridges are linear or branched and may be interrupted by at least one N or O atom. Preferred are C1-C12alkylene bridges, more preferably of C2-C6alkylene bridges like ethylene, propylene, butylene, pentylene, hexylene. C2-C12alkylene bridges interrupted by at least one N or O atom are, for example, -CH2-O-CH2-CH2, -Cn2-O-CH2-CH2-CH2, -CH2-O-CH2"CH2~CH2-CH2--CH2-O-CH2-CH2-O-CH2-. -CH2-NH-CH2-CH2. -CH2-NH-CH2-CH2-CH2, -CH2-NH-CH2-CH2-CH2-CH-,-CH2-NH-CH2-CH2-NH-CH2- or -CH2-NH-CH2-CH2-O-CH2-. C6-C12arylene is, for example, 0-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene. Preferably R1 and R2 are hydrogen or C1-C4alkyl, more preferably hydrogen or methyL Preferably R3, R4 and R5 are hydrogen or C1-C4alkyl. The radical A derived from the group A can be a stable open chain nitroxyl radical or a cyclic nitroxyl radical. Preferred is a stable cyclic nitroxyl radical. Preferably the structural element N-O are part of a 5 to 7-membered heterocyclic ring. which optionally has an additional nitrogen or oxygen atom in the ring system. Substituted piperidine, morpholine and piperazine derivatives are particularly useful. Preferably the structural element N-O is a structural element of formula (X) wherein G1, G2. G3, G4 are independently C1-C6alkyl or Gi and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12cycloalkyl group; G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl; In particular the structural element of formula (X) is of formula A, B or O described below and thus a preferred compound of the formula (1) or (II); or (la), (lla) or (llb) is a compound wherein R1 and R2 independently of one another are hydrogen or C1-C18-alkyl. R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl; R6 is hydrogen or C1-C18alkyl; X is O, NH or NR7, wherein R7 is C1-C18alkyl, Y is a direct bond or C1-C30alkylene A is a residue of formula A, B or O, wherein R8 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycldyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; R9 is C1-C18alkyl. C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; R10 is C1-C12alkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-C18alkanoyI, C3-C5 alkenoyl or benzoyl; G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or C1-C4alkyl. Especially preferred is a compound of the formula (I) or (II) or of the formula (la), (lla) or (llb) wherein R1 and R2 independently of one another are hydrogen or C1-C18-alkyl, R3, R4 and R5 is hydrogen, R6 is hydrogen, X is O, Y is C1-C30alkylene A is a residue of formula 0, More preferably in formula (Xa), (Xb), (Xc), (Xd), (Xe) and (Xf) at least two of R201. R202- R203 and R204 are ethyl, propyl or butyl and the remaining are methyl; or R201 and R202 or R203 and R204 together with the linking carbon atom form a C5-C6cycloalkyl radical and one of the remaining substituents is ethyl, propyl or butyl. The above compounds and their preparation are described in GB 2342649. Further suitable compounds are the 4-imino compounds of formula (Xi) (XI) wherein G11, G12, G13 and G14 are independently C1-C4alkyl or Gn and G12 together and G13 and Gu together, or G11 and G12 together or G13 and G14 together are pentamethylene; G15 and G16 are each independently of the other hydrogen or C1-C4alkyl; k is 1, 2, 3, or 4 Y is O, NR302 or when n is 1 and R301 represents alkyl or aryl Y is additionally a direct bond; R302 is H, C1-C18alkyl or phenyl; if k is 1 R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-Csalkoxycarbonyl; C5-C12cycloalkyl or C5-C12cycloalkenyl; phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C36alkyl, halogen, OH, C1-Csalkoxy, carboxy, C1-C8alkoxycarbonyl; -C(O)-C1-C36alkyl, or an acyl moiety of a a.p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; -SOg'Q', "P0(0"Q+)2, -P(O)(OR 2)2. -SO2-R2, -CO-NH-R2, -CONH2, COOR2. or Si(Me)3, wherein Q+ is H+, ammonium or an alkali metal cation; if k is 2 R301 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; or xylylene; or R301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms; if k is 3, R301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and if k is 4, R301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid. Preferably G16 is hydrogen and G15 is hydrogen or C1-C4alkyl, in particular methyl, and G11 and G13 are methyl and G12 and G14 are ethyl or propyl or G11 and G12 are methyl and G13 and G14 are ethyl or propyl. The 4 imino compounds of formula (XI) can be prepared for example according to E.G. Rozantsev, A.V. Chudinov, V.D.Sholle.:lzv. Akad. Nauk. SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group. The compounds are described in WO 02/100831 (Ciba). Concerning the nitroxyl radicals the alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl. butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl. Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl. 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 6 carbon atoms. Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl ( —CH2-C=CH ), 2-butinyl, 3-butinyl, n-2-octinyl, or n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atonns. Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butyl or hydroxy hexyl. Examples for halogen substituted alkyl are dichloropropyl, monobromobutyl ortrichlorohexyl. C2-Ci8alkyl interrupted by at least one 0 atom is for example -CH2-CH2-O-CH2-CH3, -CH2-CH2-O-CH3- or -CH2-CH2-0"CH2-CH2-CH2-O-CH2'CH3-. It is preferably derived from polyethlene glycol. A general description is -((CH2)a-0)b-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10. C2-C18alkyl interrupted by at least one NR5 group may be generally described as -((CH2)a-NR5)b-H/CH3, wherein a, b and R5 are as defined above. C3-C12Cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl. C6-C10 aryl is for example phenyl or naphthyl, but also comprised are C1-C4alkyl substituted phenyl, C1-C4alkoxy substituted phenyl, hydroxy, halogen or nitro substituted phenyl. Examples for alkyl substituted phenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene or isopropylbenzene. Halogen substituted phenyl is for example dichlorobenzene or bromotoluene. Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy and their corresponding isomers. Cy-Cgphenyialkyl is benzyl, phenylethyl or phenylpropyl. C5-Cioheteroaryl is for example pyrrol, pyrazol, imidazol, 2, 4, dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, thazol, pyridine, a-picoline, pyridazine, pyrazine or pyrimidine. If R is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or (3-(3,5-d(-tert-butyl-4-hydroxyphenyl)propionyl radical. CrCiBalkanoyI is for example, formyl, propionyl, butyryl, octanoyi, dodecanoyi but preferably acetyl and Cs-Csalkenoyl is in particular acryloyl. Preparation 1. Preparation of the compounds of formula I The nitroxyl radicals which are the precursors of the group A of formula (1) -(VI) are known and may be prepared according to WO 99/03984, (Ciba) EP-A-0 891 986 (Ciba) or WO 98/13392 (Akzo). The preparation of compounds of formula (I) or (II) can be performed by reacting nitroxyl radicals A* with the following carbon centered radicals: One, but not the only one, possibility is the reaction of the nitroxides A* with the following halogen derivatives transition metal such as for example Cu or Cu(l) salt, for example CuCI or CuBr, and optionally suitable ligand, for example 2,2' bipyridyl or pentamethyldiethylenetriamine. See K. Matyjaszewski, B. E. Woodworth, X. Zhang, Scott G. Gaynor, Z. Metzner.: Macromolecules 31, 5955-5957 (1998). The above halogen derivatives can be easily prepared by well-known organic reactions, for example acylation of the corresponding alcohols or amines with suitable haloacid derivatives. Examples Example 1: Preparation of a,o-Poly-(n-butyl acrylate)-co-(polysiloxane) [A-B-A structure] In a 100 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 6,00 g (18,4 mmol) of regulator A* [structure see below], 13,0 g (18,2 mmol) of an a,o-dihydrogen dimethylpolysiloxane [Mn - 1428 g/mol; SiH = 1,4 mmol/g] and 20 g of xylene are mixed and degassed twice. The clear solution obtained is heated under nitrogen to 90 °C. At this temperature 20 mg of hexachloroplatinic acid solution [0,01 mmol Pt /g i-propanol] is injected. A slightly exothermic reaction is observed. The hydrosilylation Is carried out to a residual SiH-value GPC:Mn=6018g/mol; Mw= 7798 g/mol PD = 1,29 Example 2: Preparation of Poly-(n-butyl acrylate)-co-(polysiloxane) [Comb structure] In a 100 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 2,60 g (8,0 mmol) of regulator A) [structure see above, 5,0 g (16,0 mmol) of a comb-like H-dimethylpolysiloxane [Mn / 1500 g/mol; SiH = 3,2 mmol/g] and 20 g of xylene are mixed and degassed twice. The clear solution obtained is heated under nitrogen to 80 °C. At this temperature 20 mg of hexachloroplatinic acid solution [0,01 mmol Pt /g i-propanol] is injected. A slightly exothermic reaction is observed. The residual SiH content is reacted away by addition of octene. The hydrosilylation is carried out to a residual SiH-value GPC:Mn= 7775 g/mol; Mw= 11042 g/molPD = 1,42 C': comb-like siloxanes (i.e. - [(Me)2SiO]n[MeSiHO]m-) L : a,o-clihydrogen siloxanes (i,e. HMe2SiO[(Me)2SiO]n[Me2SiH) [Mn/Mw/PD]*; mol weight distribution/polydlspersity APPLICATION RESULTS Anti crater performance A Anti crater performance in 2 pacic PU 1) Formulation 2 pack Poiyurethane Table 1 The products 1 till 3 are shaken for 5 min in a skandex shaker. After shaken, position number 4 is added and mixed in homogeneously. Positions 1 to 3 are agitated homogeneously by spatula. After mixing, let the samples rest for 1 hour before preparing the draw down. 3) Application Draw downs are prepared using a 75 pm wire bar. B Slip performance in Stoving enamel 2) Formulations for slip performance tests of the siloxane modified acrylic leveling agent: 3) Preparation of the draw downs: Draw downs of 75 pm are prepared on plastic films. The draw downs have to rest for 10 minutes before curing. Bake out time 30 min @135 °C. 4) Results Coefficient of friction: Claims 1. A compound of formula (1) or (II) wherein A is a group capable of forming a stable free nitroxyl radical A. which is bound via its oxygen atom to the carbon atom; R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyl or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring; R6 is hydrogen or C1-C18alkyl or phenyl; X is O, NH or NR7, wherein R7 is C1-C18alkyl, C3-C8cycloalkyl or phenyl; Y is a direct bond, C1-C30alkylene or C6-C12arylene, with the proviso that the compound of formula I is not wherein A, R1, R2, R3, R4, R5, R6, X and Y independently of one another are as defined in clainn 1 a is 1 or 2, or a whole number between 1 and 100, W is a linear or branched monofunctional, difunctional or multifunctional polysiloxane residue. 4- A compound of the formula (I) or (II) of claim 1 or the formula (la), (lla) or (lib) of claim 2 wherein R1 and R2 independently of one another are hydrogen or C1-C18-alkyl, R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl; Re is hydrogen or C1-C18alkyl; X is O, NH or NRy, wherein R7 is C1-C18aikyl, Y is a direct bond or C1-C30alkylene A is a residue of formula A, B or O. R8 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; R9 is C1-C18alkyl, C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; R10 is C1-C12alkyl, C5-C7cycloalkyl, C5-C8aralkyl, C2-C18alkanoyl, C3-C8alkenoyI or benzoyl; G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or C1-C4alkyl. 5. A compound of the formula (1) or (II) of claim 1 or of the formula (la), (Ha) or (lib) of claim 2 wherein R1 and R2 independently of one another are hydrogen or C1-C18-alkyl, R3, R4 and R5 is hydrogen, R6 is hydrogen, X is 0, Y is C1-C30alkylene, A is a residue of formula O G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or C1-C4alkyl. 6. A siloxane modified polymer or copolymer which is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (!) or (II) as defined in claim 1 under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la), (Ha) or (llb) as defined in claim 2, b) reacting the resulting alkoxyamine functional polysiloxane polysiloxanes (la), (lla) or (llb) with at least one vinylic monomer at a temperature between 60 and 160° C. 7. The use of a siloxane modified polymer or copolymer which is obtained as described in claim 6 as slip and leveling agent or as dispersant. 8. The use of a siloxane modified polymer or copolymer which is obtained as described in claim 6 and wherein the vinylic monomer is selected from methylacrylate, ethylacrylate, ethylhexylacrylate, propylacrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate, styrene, vinylpyridine as slip and leveling agent. 9. The use of a siloxane modified polymer or copolymer as slip and leveling agent or as dispersant, whereby the polymer or copolymer is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (III), (IV), (V) or (VI) wherein A, R1, R2, R3, R4, R5. Re. X and Y, W, a are as defined above under formula (I) b)reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer at a temperature between 60 and 160° C. Claims 1. A compound of formula (1) or (II) wherein A is a group capable of forming a stable free nitroxyl radical A. which is bound via its oxygen atom to the carbon atom; R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyl or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring; R6 is hydrogen or C1-C18alkyl or phenyl; X is O, NH or NR7, wherein R7 is C1-C18alkyl, C3-C8cycloalkyl or phenyl; Y is a direct bond, C1-C30alkylene or C6-C12arylene, with the proviso that the compound of formula I is not wherein A, R1, R2, R3, R4, R5, R6, X and Y independently of one another are as defined in clainn 1 a is 1 or 2, or a whole number between 1 and 100, W is a linear or branched monofunctional, difunctional or multifunctional polysiloxane residue. 4- A compound of the formula (I) or (II) of claim 1 or the formula (la), (lla) or (lib) of claim 2 wherein R1 and R2 independently of one another are hydrogen or C1-C18-alkyl, R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl; Re is hydrogen or C1-C18alkyl; X is O, NH or NRy, wherein R7 is C1-C18aikyl, Y is a direct bond or C1-C30alkylene A is a residue of formula A, B or O. R8 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; R9 is C1-C18alkyl, C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; R10 is C1-C12alkyl, C5-C7cycloalkyl, C5-C8aralkyl, C2-C18alkanoyl, C3-C8alkenoyI or benzoyl; G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or C1-C4alkyl. 5. A compound of the formula (1) or (II) of claim 1 or of the formula (la), (Ha) or (lib) of claim 2 wherein R1 and R2 independently of one another are hydrogen or C1-C18-alkyl, R3, R4 and R5 is hydrogen, R6 is hydrogen, X is 0, Y is C1-C30alkylene, A is a residue of formula O G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or C1-C4alkyl. 6. A siloxane modified polymer or copolymer which is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (!) or (II) as defined in claim 1 under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la), (Ha) or (llb) as defined in claim 2, b) reacting the resulting alkoxyamine functional polysiloxane polysiloxanes (la), (lla) or (llb) with at least one vinylic monomer at a temperature between 60 and 160° C. 7. The use of a siloxane modified polymer or copolymer which is obtained as described in claim 6 as slip and leveling agent or as dispersant. 8. The use of a siloxane modified polymer or copolymer which is obtained as described in claim 6 and wherein the vinylic monomer is selected from methylacrylate, ethylacrylate, ethylhexylacrylate, propylacrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate, styrene, vinylpyridine as slip and leveling agent. 9. The use of a siloxane modified polymer or copolymer as slip and leveling agent or as dispersant, whereby the polymer or copolymer is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (III), (IV), (V) or (VI) wherein A, R1, R2, R3, R4, R5. Re. X and Y, W, a are as defined above under formula (I) b)reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer at a temperature between 60 and 160° C.

Full Text

Novel Alkoxyamines Containing Unsaturated Groups
The invention relates to new alkoxyamines suitable for hydrosilylation reactions, to siloxane modified alkoxamines and to siloxane modified polymers as well as to their use.
The International Publication WO2004/029156 (Ciba) describes a process for the preparation of a triblock-copolymer or graft-copolymer via controlled free radical polymerization using NOR functional polysiloxanes. A polysiloxane is reacted with an ethylenically unsaturated functional alkoxyamine of formula (!)
(I) under hydrosilylation conditions. Polymers containing e.g, poly-styrol-
polysiloxane-poly-styrol blocks are obtained.
Chem. Commun., 2004, 174-175 describes radical cyclization reactions using alkoxyamines as starting material. The alkoxamines disclosed therein are disclaimed.
It has been found that using specific alkoxyamines as hydrosilylation agent, siloxane modified alkoxamines having an improved activity in polymerising acrylates can be obtained.
One aspect of the invention is a compound of formula (I) or (II)

wherein
A is a group capable of forming a stable free nitroxyl radical A. which is bound via its
oxygen atom to the carbon atom;
R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyI or
phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano,
carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino;
R3, R4 and R5 independently of one another are hydrogen or C1-C4alkyl or phenyl; or R3
and R5 together with the linking group C=C form a 5 to 12 membered ring;
R6 is hydrogen or C1-C18alkyl or phenyl;

X is O, NH or NR7, wherein R7 is C1-C18alkyl, C3-C8cycloalkyl or phenyl; Y is a direct bond, C1-C30alkylene or C6-C12arylene, with the proviso that the compound of formula I is not

wherein
A, R1, R2, R3, R4, R5. R6. X and Y independently of one another are as defined above under
formula (I) or (II) and
a is 1 or 2, or a whole number between 1 and 100,
W is a linear or branched monofunctional, difunctional or multifunctional polysiloxane
residue.
Furthermore the invention relates to a siloxane modified polymer or copolymer which is
obtained by
a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (I) or (II) as defined above under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la), (lla)or(llb)

b) reacting the resulting alkoxyamine functional polysiloxane (la), (lla) or (lib) with at least one vinylic monomer at a temperature between 60 and 160° C.
Furthermore the invention relates to the use of a siloxane modified polymer or copolymer which is obtained as described above as slip and leveling agent or as dispersant.
Furthermore the invention relates to the use of a siloxane modified polymer or copolymer as slip and leveling agent or as dispersant, whereby the polymer or copolymer is obtained by a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (III), (IV), (V) or (VI)

under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (IlIa), (IVa or IVb), (Va), (Via or VIb)

wherein A, R1, R2, R3, R4, R5, R6. X and Y, W, a are as defined above under formula (I)
c) reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic
nnonomer at a temperature between 60 and 160°C.
Preferences:
Preferred is a compound of the formula I and a siloxane modified initiator of the formula la and a siloxane modified polymer or copolymer which is obtained by
d) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (I) under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la),
e) reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer at a temperature between 60 and 160°C.
Vinylic monomers
The vinylic monomer is selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic acid (C1-C22)alkyl esters, acrylic acid (C1-C22)-hydroxyalkyl esters, methacrylic acid (C1-C22)alkyl esters, methacrylic acid (C1-C22)hydroxy-alkyl esters, acrylic acid (C1-C22)alkyl esters or methacrylic acid (C1-C22)alkyl esters which are substituted by amino, (C1-C22)alkylamino, (C1-C22)dialkylamino, -SO3H, epoxy. fluoro, perfluoro or siloxane groups, styrene, substituted styrene, acrylamide and methacrylamide. N-mono(C1-C22)alkyl acrylamide, N,N-di(C1-C22)alkyl acrylamide; provided that the amount of

unsubstituted acrylic acid (C1-C22)alkyl esters or/and methacrylic acid (C1-C22)alkyl esters is more than 30 % by weight based on the weight of the total monomer mixture.
Preferably the vinylic monomer Is styrene, methylacrylate, ethylacrylate, n-butylacrylate, iso-butylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethyl-aminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)-acryiate, hydroxyethyl(meth)acrylate. hydroxypropyl(meth)acrylate, dimethylaminoethyi-(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide. methacryiamide or dimethylaminopropyl-methacrylamide or mixtures of them.
In a preferred embodiment the vinylic monomer is an acrylic monomer.
If the siloxane modified polymer is used as slip and leveling agent the especially preferred vinylic monomer is selected from methylacrylate, ethylacrylate, ethylhexylacrylate, propyl-acrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate, styrene, vinylpyridine.
If the siloxane modified polymer is used as dispersant the especially preferred vinylic monomer is an acrylic acid (C1-C22)alkyl esters or methacrylic acid (C1-C22)alkyl esters which are substituted by amino, (C1-C22)alkylamino, (C1-C22)dialkylamino, e.g. dimethylaminoethyl-(meth)acrylate.
In the context of this invention, the term "polymer" refers to a polymer of any type including homopolymers and copolymers. The term "copolymer" is meant to include polymers containing groups or units derived from two or more monomers with random, diblock, and multi-block microstructures. The copolymer can be block(co)polymers, comb(co)polymers, star(co)polymers, dendritic(co)polymers or hyperbranched(co)polymers. Block structures such as diblock, triblock are preferred.
In other words, after completing the polymerization of a first monomer to the extent desired to form a first polymer "block", a second monomer is introduced into the reaction mass to effect polymerization of the second monomer to form a second polymer "block" that is attached to the end of the first block. Using this sequential addition process, a broad range of diblock, triblock, etc. copolymers can be prepared.

The term "copolymer" also includes gradient copolymers or tapered copolymers which are copolymers composed for example of two monomers or monomer mixtures A and B in whose individual chains there is a gradient in the distribution of the monomer units along the chains. One end of the chain is rich in A units and the other in B units. Such copolymers show a continuous transition of one monomer or monomer mixture A into another monomer of monomer mixture B along the polymer chain.
Polysiloxanes
The Si-H functionalized polysiloxane is linear or branched and is commercially available or can be produced via known methods (Silicone, Chemie und Technologie [Silicones. Chemistry and Technology], Vulkan Publishers, Essen 1989, pp 82-84).
The Si-H functionalized polysiloxanes contains at least one unit corresponding to the general formula H(R2)2SiOi/2 wherein R is C1-C6alkyl or phenyl, preferably methyl. The Si-H unit or Si-H units can be in alpha and/or omega position or can be distributed. Thus, the siloxanes are taken from the group consisting of linear siloxanes. comb-like siloxanes , T-branched siloxanes.

Definitions:
C1-C28alkyl radicals are linear or branclied and are, for example, methyl, ethyl and the various position isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl. dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.
C3-C8cycloalkyl is. for example, cyclopropyl. dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
C1-C30alkylene bridges are linear or branched and may be interrupted by at least one N or O atom. Preferred are C1-C12alkylene bridges, more preferably of C2-C6alkylene bridges like ethylene, propylene, butylene, pentylene, hexylene.
C2-C12alkylene bridges interrupted by at least one N or O atom are, for example, -CH2-O-CH2-CH2, -Cn2-O-CH2-CH2-CH2, -CH2-O-CH2"CH2~CH2-CH2--CH2-O-CH2-CH2-O-CH2-. -CH2-NH-CH2-CH2. -CH2-NH-CH2-CH2-CH2, -CH2-NH-CH2-CH2-CH2-CH-,-CH2-NH-CH2-CH2-NH-CH2- or -CH2-NH-CH2-CH2-O-CH2-.
C6-C12arylene is, for example, 0-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
Preferably R1 and R2 are hydrogen or C1-C4alkyl, more preferably hydrogen or methyL

Preferably R3, R4 and R5 are hydrogen or C1-C4alkyl.
The radical A derived from the group A can be a stable open chain nitroxyl radical or a cyclic nitroxyl radical.
Preferred is a stable cyclic nitroxyl radical.
Preferably the structural element N-O are part of a 5 to 7-membered heterocyclic ring.
which optionally has an additional nitrogen or oxygen atom in the ring system. Substituted piperidine, morpholine and piperazine derivatives are particularly useful.
Preferably the structural element N-O is a structural element of formula (X)

wherein
G1, G2. G3, G4 are independently C1-C6alkyl or Gi and G2 or G3 and G4, or G1 and G2 and G3
and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl;
In particular the structural element of formula (X) is of formula A, B or O described below and
thus a preferred compound of the formula (1) or (II); or (la), (lla) or (llb) is a compound
wherein
R1 and R2 independently of one another are hydrogen or C1-C18-alkyl.
R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl;
R6 is hydrogen or C1-C18alkyl;
X is O, NH or NR7, wherein R7 is C1-C18alkyl,
Y is a direct bond or C1-C30alkylene
A is a residue of formula A, B or O,

wherein
R8 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen
atoms, cyanoethyl, benzoyl, glycldyl, a monovalent radical of an aliphatic carboxylic acid
having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms,
or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic
carboxylic acid having 7 to 15 carbon atoms;
R9 is C1-C18alkyl. C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano,
carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(0H)-Z or of the
formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl;
R10 is C1-C12alkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-C18alkanoyI, C3-C5 alkenoyl or
benzoyl;
G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and
G4 are ethyl or propyl;
G5 is hydrogen or C1-C4alkyl.
Especially preferred is a compound of the formula (I) or (II) or of the formula (la), (lla) or (llb)
wherein
R1 and R2 independently of one another are hydrogen or C1-C18-alkyl,
R3, R4 and R5 is hydrogen,
R6 is hydrogen,
X is O,
Y is C1-C30alkylene
A is a residue of formula 0,

More preferably in formula (Xa), (Xb), (Xc), (Xd), (Xe) and (Xf) at least two of R201. R202- R203 and R204 are ethyl, propyl or butyl and the remaining are methyl; or
R201 and R202 or R203 and R204 together with the linking carbon atom form a C5-C6cycloalkyl radical and one of the remaining substituents is ethyl, propyl or butyl.
The above compounds and their preparation are described in GB 2342649. Further suitable compounds are the 4-imino compounds of formula (Xi)
(XI) wherein
G11, G12, G13 and G14 are independently C1-C4alkyl or Gn and G12 together and G13 and Gu together, or G11 and G12 together or G13 and G14 together are pentamethylene; G15 and G16 are each independently of the other hydrogen or C1-C4alkyl; k is 1, 2, 3, or 4
Y is O, NR302 or when n is 1 and R301 represents alkyl or aryl Y is additionally a direct bond; R302 is H, C1-C18alkyl or phenyl;
if k is 1
R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be
unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-Csalkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or
more C1-C36alkyl, halogen, OH, C1-Csalkoxy, carboxy, C1-C8alkoxycarbonyl;
-C(O)-C1-C36alkyl, or an acyl moiety of a a.p-unsaturated carboxylic acid having 3 to 5
carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
-SOg'Q', "P0(0"Q+)2, -P(O)(OR 2)2. -SO2-R2, -CO-NH-R2, -CONH2, COOR2. or Si(Me)3,
wherein Q+ is H+, ammonium or an alkali metal cation;
if k is 2

R301 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or
substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
or xylylene; or
R301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a
cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid;
and
if k is 4, R301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic
acid.
Preferably G16 is hydrogen and G15 is hydrogen or C1-C4alkyl, in particular methyl, and
G11 and G13 are methyl and G12 and G14 are ethyl or propyl or G11 and G12 are methyl and G13
and G14 are ethyl or propyl.
The 4 imino compounds of formula (XI) can be prepared for example according to E.G. Rozantsev, A.V. Chudinov, V.D.Sholle.:lzv. Akad. Nauk. SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group. The compounds are described in WO 02/100831 (Ciba).
Concerning the nitroxyl radicals the alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl. butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl. 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 6 carbon atoms.

Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl ( —CH2-C=CH ), 2-butinyl, 3-butinyl, n-2-octinyl, or n-2-octadecinyl. Preferred is alkinyl
with 3 to 12, particularly preferred with 3 to 6 carbon atonns.
Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butyl or hydroxy hexyl.
Examples for halogen substituted alkyl are dichloropropyl, monobromobutyl ortrichlorohexyl.
C2-Ci8alkyl interrupted by at least one 0 atom is for example -CH2-CH2-O-CH2-CH3, -CH2-CH2-O-CH3- or -CH2-CH2-0"CH2-CH2-CH2-O-CH2'CH3-. It is preferably derived from polyethlene glycol. A general description is -((CH2)a-0)b-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
C2-C18alkyl interrupted by at least one NR5 group may be generally described as -((CH2)a-NR5)b-H/CH3, wherein a, b and R5 are as defined above.
C3-C12Cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.
C6-C10 aryl is for example phenyl or naphthyl, but also comprised are C1-C4alkyl substituted phenyl, C1-C4alkoxy substituted phenyl, hydroxy, halogen or nitro substituted phenyl. Examples for alkyl substituted phenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene or isopropylbenzene. Halogen substituted phenyl is for example dichlorobenzene or bromotoluene.
Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy and their corresponding isomers.
Cy-Cgphenyialkyl is benzyl, phenylethyl or phenylpropyl.
C5-Cioheteroaryl is for example pyrrol, pyrazol, imidazol, 2, 4, dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, thazol, pyridine, a-picoline, pyridazine, pyrazine or pyrimidine.

If R is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or (3-(3,5-d(-tert-butyl-4-hydroxyphenyl)propionyl radical.
CrCiBalkanoyI is for example, formyl, propionyl, butyryl, octanoyi, dodecanoyi but preferably acetyl and Cs-Csalkenoyl is in particular acryloyl.

Preparation
1. Preparation of the compounds of formula I
The nitroxyl radicals which are the precursors of the group A of formula (1) -(VI) are known and may be prepared according to WO 99/03984, (Ciba) EP-A-0 891 986 (Ciba) or WO 98/13392 (Akzo).

The preparation of compounds of formula (I) or (II) can be performed by reacting nitroxyl radicals A* with the following carbon centered radicals:

One, but not the only one, possibility is the reaction of the nitroxides A* with the following halogen derivatives transition metal such as for example Cu or Cu(l) salt, for example CuCI or CuBr, and optionally suitable ligand, for example 2,2' bipyridyl or pentamethyldiethylenetriamine. See K. Matyjaszewski, B. E. Woodworth, X. Zhang, Scott G. Gaynor, Z. Metzner.: Macromolecules 31, 5955-5957 (1998).

The above halogen derivatives can be easily prepared by well-known organic reactions, for example acylation of the corresponding alcohols or amines with suitable haloacid derivatives.
Examples
Example 1: Preparation of a,o-Poly-(n-butyl acrylate)-co-(polysiloxane) [A-B-A structure]
In a 100 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 6,00 g (18,4 mmol) of regulator A* [structure see below], 13,0 g (18,2 mmol) of an a,o-dihydrogen dimethylpolysiloxane [Mn - 1428 g/mol; SiH = 1,4 mmol/g] and 20 g of xylene are mixed and degassed twice. The clear solution obtained is heated under nitrogen to 90 °C. At this temperature 20 mg of hexachloroplatinic acid solution [0,01 mmol Pt /g i-propanol] is

injected. A slightly exothermic reaction is observed. The hydrosilylation Is carried out to a residual SiH-value GPC:Mn=6018g/mol; Mw= 7798 g/mol PD = 1,29

Example 2: Preparation of Poly-(n-butyl acrylate)-co-(polysiloxane) [Comb structure]
In a 100 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 2,60 g (8,0 mmol) of regulator A*) [structure see above, 5,0 g (16,0 mmol) of a comb-like H-dimethylpolysiloxane [Mn / 1500 g/mol; SiH = 3,2 mmol/g] and 20 g of xylene are mixed and degassed twice. The clear solution obtained is heated under nitrogen to 80 °C. At this temperature 20 mg of hexachloroplatinic acid solution [0,01 mmol Pt /g i-propanol] is injected. A slightly exothermic reaction is observed. The residual SiH content is reacted away by addition of octene. The hydrosilylation is carried out to a residual SiH-value GPC:Mn= 7775 g/mol; Mw= 11042 g/molPD = 1,42

C': comb-like siloxanes (i.e. - [(Me)2SiO]n[MeSiHO]m-)
L *: a,o-clihydrogen siloxanes (i,e. HMe2SiO[(Me)2SiO]n[Me2SiH)
[Mn/Mw/PD]*; mol weight distribution/polydlspersity
APPLICATION RESULTS
Anti crater performance
A Anti crater performance in 2 pacic PU
1) Formulation 2 pack Poiyurethane Table 1

The products 1 till 3 are shaken for 5 min in a skandex shaker. After shaken, position number 4 is added and mixed in homogeneously.

Positions 1 to 3 are agitated homogeneously by spatula.
After mixing, let the samples rest for 1 hour before preparing the draw down.
3) Application Draw downs are prepared using a 75 pm wire bar.

B Slip performance in Stoving enamel

2) Formulations for slip performance tests of the siloxane modified acrylic leveling agent:

3) Preparation of the draw downs:
Draw downs of 75 pm are prepared on plastic films.
The draw downs have to rest for 10 minutes before curing.
Bake out time 30 min @135 °C.
4) Results Coefficient of friction:

Claims
1. A compound of formula (1) or (II)

wherein
A is a group capable of forming a stable free nitroxyl radical A. which is bound via its
oxygen atom to the carbon atom;
R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyl or
phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano,
carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino;
R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl or phenyl; or R3
and R5 together with the linking group C=C form a 5 to 12 membered ring;
R6 is hydrogen or C1-C18alkyl or phenyl;
X is O, NH or NR7, wherein R7 is C1-C18alkyl, C3-C8cycloalkyl or phenyl;
Y is a direct bond, C1-C30alkylene or C6-C12arylene,
with the proviso that the compound of formula I is not

wherein
A, R1, R2, R3, R4, R5, R6, X and Y independently of one another are as defined in clainn 1
a is 1 or 2, or a whole number between 1 and 100,
W is a linear or branched monofunctional, difunctional or multifunctional polysiloxane
residue.

4- A compound of the formula (I) or (II) of claim 1 or the formula (la), (lla) or (lib) of claim 2
wherein
R1 and R2 independently of one another are hydrogen or C1-C18-alkyl,
R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl;

Re is hydrogen or C1-C18alkyl;
X is O, NH or NRy, wherein R7 is C1-C18aikyl,
Y is a direct bond or C1-C30alkylene
A is a residue of formula A, B or O.

R8 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen
atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid
having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms,
or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic
carboxylic acid having 7 to 15 carbon atoms;
R9 is C1-C18alkyl, C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano,
carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the
formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl;
R10 is C1-C12alkyl, C5-C7cycloalkyl, C5-C8aralkyl, C2-C18alkanoyl, C3-C8alkenoyI or
benzoyl;
G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and
G4 are ethyl or propyl;
G5 is hydrogen or C1-C4alkyl.
5. A compound of the formula (1) or (II) of claim 1 or of the formula (la), (Ha) or (lib) of claim 2
wherein
R1 and R2 independently of one another are hydrogen or C1-C18-alkyl,
R3, R4 and R5 is hydrogen,
R6 is hydrogen,
X is 0,
Y is C1-C30alkylene,
A is a residue of formula O

G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and
G4 are ethyl or propyl;
G5 is hydrogen or C1-C4alkyl.
6. A siloxane modified polymer or copolymer which is obtained by
a) reacting a Si-H functionalized polysiloxane in the presence of a functional
alkoxyamine initiator/regulator compound of the formula (!) or (II) as defined in claim 1
under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la),
(Ha) or (llb) as defined in claim 2,
b) reacting the resulting alkoxyamine functional polysiloxane polysiloxanes (la), (lla) or
(llb) with at least one vinylic monomer at a temperature between 60 and 160° C.
7. The use of a siloxane modified polymer or copolymer which is obtained as described in
claim 6 as slip and leveling agent or as dispersant.
8. The use of a siloxane modified polymer or copolymer which is obtained as described in
claim 6 and wherein the vinylic monomer is selected from methylacrylate, ethylacrylate,
ethylhexylacrylate, propylacrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate,
styrene, vinylpyridine as slip and leveling agent.
9. The use of a siloxane modified polymer or copolymer as slip and leveling agent or as
dispersant, whereby the polymer or copolymer is obtained by
a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (III), (IV), (V) or (VI)

wherein A, R1, R2, R3, R4, R5. Re. X and Y, W, a are as defined above under formula (I) b)reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer at a temperature between 60 and 160° C.

Claims
1. A compound of formula (1) or (II)

wherein
A is a group capable of forming a stable free nitroxyl radical A. which is bound via its
oxygen atom to the carbon atom;
R1 and R2 independently of one another are hydrogen, C1-C18-alkyl, C3-C8cycloalkyl or
phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano,
carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino;
R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl or phenyl; or R3
and R5 together with the linking group C=C form a 5 to 12 membered ring;
R6 is hydrogen or C1-C18alkyl or phenyl;
X is O, NH or NR7, wherein R7 is C1-C18alkyl, C3-C8cycloalkyl or phenyl;
Y is a direct bond, C1-C30alkylene or C6-C12arylene,
with the proviso that the compound of formula I is not

wherein
A, R1, R2, R3, R4, R5, R6, X and Y independently of one another are as defined in clainn 1
a is 1 or 2, or a whole number between 1 and 100,
W is a linear or branched monofunctional, difunctional or multifunctional polysiloxane
residue.

4- A compound of the formula (I) or (II) of claim 1 or the formula (la), (lla) or (lib) of claim 2
wherein
R1 and R2 independently of one another are hydrogen or C1-C18-alkyl,
R3, R4 and R5 independently of one another are hydrogen or C1-C18alkyl;

Re is hydrogen or C1-C18alkyl;
X is O, NH or NRy, wherein R7 is C1-C18aikyl,
Y is a direct bond or C1-C30alkylene
A is a residue of formula A, B or O.

R8 is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen
atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid
having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms,
or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic
carboxylic acid having 7 to 15 carbon atoms;
R9 is C1-C18alkyl, C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano,
carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the
formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl;
R10 is C1-C12alkyl, C5-C7cycloalkyl, C5-C8aralkyl, C2-C18alkanoyl, C3-C8alkenoyI or
benzoyl;
G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and
G4 are ethyl or propyl;
G5 is hydrogen or C1-C4alkyl.
5. A compound of the formula (1) or (II) of claim 1 or of the formula (la), (Ha) or (lib) of claim 2
wherein
R1 and R2 independently of one another are hydrogen or C1-C18-alkyl,
R3, R4 and R5 is hydrogen,
R6 is hydrogen,
X is 0,
Y is C1-C30alkylene,
A is a residue of formula O

G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and
G4 are ethyl or propyl;
G5 is hydrogen or C1-C4alkyl.
6. A siloxane modified polymer or copolymer which is obtained by
a) reacting a Si-H functionalized polysiloxane in the presence of a functional
alkoxyamine initiator/regulator compound of the formula (!) or (II) as defined in claim 1
under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (la),
(Ha) or (llb) as defined in claim 2,
b) reacting the resulting alkoxyamine functional polysiloxane polysiloxanes (la), (lla) or
(llb) with at least one vinylic monomer at a temperature between 60 and 160° C.
7. The use of a siloxane modified polymer or copolymer which is obtained as described in
claim 6 as slip and leveling agent or as dispersant.
8. The use of a siloxane modified polymer or copolymer which is obtained as described in
claim 6 and wherein the vinylic monomer is selected from methylacrylate, ethylacrylate,
ethylhexylacrylate, propylacrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate,
styrene, vinylpyridine as slip and leveling agent.
9. The use of a siloxane modified polymer or copolymer as slip and leveling agent or as
dispersant, whereby the polymer or copolymer is obtained by
a) reacting a Si-H functionalized polysiloxane in the presence of a functional alkoxyamine initiator/regulator compound of the formula (III), (IV), (V) or (VI)

wherein A, R1, R2, R3, R4, R5. Re. X and Y, W, a are as defined above under formula (I) b)reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer at a temperature between 60 and 160° C.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=sCoA0k1cVLXb/qQ9nf2voQ==&loc=egcICQiyoj82NGgGrC5ChA==

« Previous Patent

Next Patent »

Patent Number

269228

Indian Patent Application Number

2061/CHENP/2008

PG Journal Number

42/2015

Publication Date

16-Oct-2015

Grant Date

12-Oct-2015

Date of Filing

25-Apr-2008

Name of Patentee

BASF SE

Applicant Address

67056, LUDWIGSHAFEN, GERMANY

Inventors:

#	Inventor's Name	Inventor's Address
1	ENGELBRECHT, LOTHAR, ALEXANDER	BUIZERD 52 NL-8446 KL HEERENVEEN
2	NESVADBA, PETER	ROUTE DES PRALETTES 83A CH-1723 MARLY

PCT International Classification Number

C08G77/10

PCT International Application Number

PCT/EP06/67410

PCT International Filing date

2006-10-16

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	05110005.5	2005-10-26	EUROPEAN UNION