WO2007048719A1 - Novel alkoxyamines containing unsaturated groups - Google Patents

Novel alkoxyamines containing unsaturated groups Download PDF

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Publication number
WO2007048719A1
WO2007048719A1 PCT/EP2006/067410 EP2006067410W WO2007048719A1 WO 2007048719 A1 WO2007048719 A1 WO 2007048719A1 EP 2006067410 W EP2006067410 W EP 2006067410W WO 2007048719 A1 WO2007048719 A1 WO 2007048719A1
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Prior art keywords
alkyl
formula
hydrogen
phenyl
independently
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PCT/EP2006/067410
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French (fr)
Inventor
Lothar Alexander Engelbrecht
Peter Nesvadba
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Ciba Holding Inc.
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Priority to US12/084,022 priority Critical patent/US7812100B2/en
Priority to JP2008537050A priority patent/JP5205270B2/en
Priority to CN2006800400559A priority patent/CN101296969B/en
Priority to EP06819077.6A priority patent/EP1940919B1/en
Priority to KR1020087012564A priority patent/KR101365954B1/en
Publication of WO2007048719A1 publication Critical patent/WO2007048719A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/10—Equilibration processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen

Definitions

  • 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.
  • Ciba 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)
  • polysiloxane-poly-styrol blocks are obtained.
  • 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)
  • A is a group capable of forming a stable free nitroxyl radical A* which is bound via its oxygen atom to the carbon atom;
  • R 1 and R 2 independently of one another are hydrogen, Ci-Ci 8 -alkyl, QrC ⁇ cycloalkyl or phenyl which are unsubstituted or substituted by NO 2 , halogen, amino, hydroxy, cyano, carboxy, CrC 4 alkoxy, CrC 4 alkylthio, Ci-C 4 alkylamino or di(Ci-C 4 alkyl)amino;
  • R 6 is hydrogen or CrCi 8 alkyl or phenyl
  • X is O, NH or NR 7 , wherein R 7 is Ci-Ci ⁇ alkyl, C 3 -C ⁇ cycloalkyl or phenyl
  • Y is a direct bond, CrC 30 alkylene or C 6 -Ci 2 arylene, with the proviso that the compound of formula I is not
  • Another aspect of the invention is a polysiloxane modified initiator/regulator of the formula
  • R 1 , R 2 , R3, R 4 , R5, Re, 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.
  • 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 (Ia), (Ma) or (lib) b) reacting the resulting alkoxyamine functional polysiloxane (Ia), (Ma) or (Mb) with at least one vinylic monomer at a temperature between 60 and 160° C.
  • 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.
  • 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 (Vl)
  • the vinylic monomer is selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic acid (CrC 22 )alkyl esters, acrylic acid (C 1 -C 22 )- hydroxyalkyl esters, methacrylic acid (CrC 22 )alkyl esters, methacrylic acid (C- ⁇ -C 22 )hydroxy- alkyl esters, acrylic acid (CrC 22 )alkyl esters or methacrylic acid (CrC 22 )alkyl esters which are substituted by amino, (Ci-C 22 )alkylamino, (Ci-C 22 )dialkylamino, -SO 3 H, epoxy, fluoro, perfluoro or siloxane groups, styrene, substituted styrene, acrylamide and methacrylamide, N-mono(Ci-C 22 )alkyl acrylamide, N,N-di(CrC
  • 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)- acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl- (meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl-methacrylamide or mixtures of them.
  • the vinylic monomer is an acrylic monomer.
  • the especially preferred vinylic monomer is selected from methylacrylate, ethylacrylate, ethylhexylacrylate, propyl- acrylate, cyclohexylacrylate, hydroxyethylacrylate, n-butylacrylate, styrene, vinylpyridine.
  • the especially preferred vinylic monomer is an acrylic acid (CrC 22 )alkyl esters or methacrylic acid (CrC 22 )alkyl esters which are substituted by amino, (Ci-C 22 )alkylamino, (Ci-C 22 )dialkylamino, e.g. dimethylaminoethyl- (meth)acrylate.
  • polymer refers to a polymer of any type including homopolymers and copolymers.
  • 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.
  • 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.
  • 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(R 2 ) 2 Si0i /2 wherein R is CrC 6 alkyl or phenyl, preferably methyl.
  • the Si-H unit or Si-H units can be in alpha and/or omega position or can be distributed.
  • the siloxanes are taken from the group consisting of linear siloxanes, comb-like siloxanes , T-branched siloxanes.
  • CrC 2 8alkyl radicals are linear or branched 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.
  • Cs-C ⁇ cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • CrC 30 alkylene bridges are linear or branched and may be interrupted by at least one N or O atom.
  • Preferred are CrC ⁇ alkylene bridges, more preferably of C 2 -C6alkylene bridges like ethylene, propylene, butylene, pentylene, hexylene.
  • C 2 -Ci 2 alkylene bridges interrupted by at least one N or O atom are, for example, -CH 2 -O-CH 2 -CH 2 , -CH 2 -O-CH 2 -CH 2 -CH 2 , -CH 2 -O-CH 2 -CH 2 -CH 2 -, -CH 2 -O-CH 2 -CH 2 -O-CH2-, -CH 2 -NH-CH 2 -CH 2 , -CH 2 -NH-CH 2 -CH 2 -CH 2 , -CH 2 -NH-CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -NH-CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -NH-CH 2 -CH 2 -NH-C ⁇ - or -CH 2 -N H-CH 2 -CH 2 -O-CH2-.
  • C6-C"i 2 arylene is, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
  • Ri and R 2 are hydrogen or d-C 4 alkyl, more preferably hydrogen or methyl.
  • R 3 , R 4 and R 5 are hydrogen or d-C 4 alkyl.
  • 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.
  • the structural element N-O* are part of a 5 to 7-membered heterocyclic ring,
  • the structural element N-O* is a structural element of formula (X)
  • Gi, G 2 , G 3 , G 4 are independently CrC 6 alkyl or Gi and G 2 or G 3 and G 4 , or Gi and G 2 and G 3 and G 4 together form a C 5 -Ci 2 cycloalkyl group;
  • G 5 , G 6 independently are H, CrCi 8 alkyl, phenyl, naphthyl or a group COOCrCi 8 alkyl;
  • R 1 and R 2 independently of one another are hydrogen or Ci-Ci 8 -alkyl
  • R 3 , R 4 and R 5 independently of one another are hydrogen or d-Ci ⁇ alkyl
  • R 6 is hydrogen or CrCi 8 alkyl
  • X is O, NH or NR 7 , wherein R 7 is C r Ci 8 alkyl,
  • Y is a direct bond or CrC 30 alkylene
  • A is a residue of formula A, B or O, wherein
  • R 8 is hydrogen, d-Ci 8 alkyl 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 ⁇ , ⁇ -unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
  • Rg is CrCiealkyl, C 5 -C 7 cycloalkyl, C 2 -Cealkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH 2 CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl;
  • R 10 is Ci-Ci 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -Ci 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl;
  • Gi and G 3 are methyl and G 2 and G 4 are ethyl or propyl or d and G 2 are methyl and G 3 and
  • G 4 are ethyl or propyl; G 5 is hydrogen or CrC 4 alkyl.
  • R 3 , R 4 and R 5 is hydrogen
  • R 6 is hydrogen
  • Y is CrC 30 alkylene
  • A is a residue of formula O
  • Gi and G3 are methyl and G 2 and G 4 are ethyl or propyl or d and G 2 are methyl and G3 and
  • G 4 are ethyl or propyl
  • G 5 is hydrogen or d-C 4 alkyl.
  • Another preferred structural element of formula (X) are those of formula (Xa), (Xb), (Xc), (Xd), (Xe) or (Xf)
  • R 2 oi, R 202 , R 203 and R 204 independently of each other are CrCi 8 alkyl, C 3 -Ci 8 alkenyl, C 3 -Ci 8 alkinyl, CrCi 8 alkyl, C 3 -Ci 8 alkenyl, C 3 -Ci 8 alkinyl which are substituted by OH, halogen or a group -0-C(O)-R 2O s, C 2 -Ci 8 alkyl which is interrupted by at least one O atom and/or NR 20S group, C 3 -Ci 2 cycloalkyl or C 6 -Ci 0 aryl or R 201 and R 202 and/or R 203 and R 204 together with the linking carbon atom form a C 3 -Ci 2 cycloalkyl radical; R 205 , R 206 and R 207 independently are hydrogen, Ci-Ci 8 alkyl or C 6 -Ci 0 aryl; R 208 is
  • R 2 oi, R202, R203 and R 2 0 4 are ethyl, propyl or butyl and the remaining are methyl; or
  • R 2 0 1 and R 2 0 2 or R 2 03 and R 204 together with the linking carbon atom form a C 5 -C 6 cycloalkyl radical and one of the remaining substituents is ethyl, propyl or butyl.
  • G 11 , G 12 , G 13 and G 14 are independently CrC 4 alkyl or G 11 and G 12 together and G 13 and G 14 together, or G 11 and G 12 together or G 13 and G 14 together are pentamethylene;
  • G 15 and G 16 are each independently of the other hydrogen or Ci-C 4 alkyl;
  • k is 1 , 2, 3, or 4
  • Y is O, NR 302 or when n is 1 and R 301 represents alkyl or aryl Y is additionally a direct bond; R 302 is H, CrC 18 alkyl or phenyl;
  • R 301 is H, straight or branched CrC 18 alkyl, C 3 -C 18 alkenyl or C 3 -C 18 alkinyl, which may be unsubstituted or substituted, by one or more OH, C- ⁇ -C 8 alkoxy, carboxy, C- ⁇ -C 8 alkoxycarbonyl;
  • C 5 -C 12 cycloalkyl or C 5 -C 12 cycloalkenyl phenyl, C 7 -C 9 phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more CrC 8 alkyl, halogen, OH, CrC 8 alkoxy, carboxy, C- ⁇ -C 8 alkoxycarbonyl; -C(O)-C- ⁇ -C 3 6alkyl, or an acyl moiety of a ⁇ , ⁇ -unsatu rated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
  • R 3 oi is CrCi 8 alkylene, C 3 -Ci 8 alkenylene or C 3 -Ci 8 alkinylene, which may be unsubstituted or substituted, by one or more OH, d-C ⁇ alkoxy, carboxy, C-i-C ⁇ alkoxycarbonyl; or xylylene; or
  • R 3 oi 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;
  • R 3 oi is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and if k is 4, R 3 oi is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
  • d ⁇ is hydrogen and Gi 5 is hydrogen or Ci-C 4 alkyl, in particular methyl, and Gii and Gi 3 are methyl and Gi 2 and Gi 4 are ethyl or propyl or Gn and Gi 2 are methyl and Gi 3 and Gi 4 are ethyl or propyl.
  • the 4 imino compounds of formula (Xl) 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).
  • alkyl radicals in the various substituents may be linear or branched.
  • 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.
  • alkenyl with 3 bis 12, particularly preferred with 3 to 6 carbon atoms is Preferred.
  • Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl
  • alkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
  • hydroxy substituted alkyl examples are hydroxy propyl, hydroxy butyl or hydroxy hexyl.
  • halogen substituted alkyl examples include dichloropropyl, monobromobutyl or trichlorohexyl.
  • C 2 -Ci 8 alkyl interrupted by at least one O atom is for example -CH 2 -CH 2 -O-CH 2 -CH 3 , -CH 2 - CH 2 -O-CH 3 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3 -. It is preferably derived from polyethlene glycol.
  • a general description is -((CH 2 ) a -O) t ,-H/CH 3 , wherein a is a number from 1 to 6 and b is a number from 2 to 10.
  • C 2 -Ci 8 alkyl interrupted by at least one NR 5 group may be generally described as -((CH 2 ) a - NR 5 ) b -H/CH 3 , wherein a, b and R 5 are as defined above.
  • C 3 -Ci 2 cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.
  • C 6 -Ci 0 aryl is for example phenyl or naphthyl, but also comprised are CrC 4 alkyl substituted phenyl, Ci-C 4 alkoxy substituted phenyl, hydroxy, halogen or nitro substituted phenyl.
  • 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.
  • C 7 -C 9 phenylalkyl is benzyl, phenylethyl or phenylpropyl.
  • C 5 -Ci 0 heteroaryl is for example pyrrol, pyrazol, imidazol, 2, 4, dimethylpyrrol, 1 -methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine, ⁇ -picoline, pyridazine, pyrazine or pyrimidine.
  • 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 ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
  • CrCi 8 alkanoyl is for example, formyl, propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl and C3-C 5 alkenoyl is in particular acryloyl.
  • nitroxyl radicals are those of formulae
  • nitroxyl radicals which are the precursors of the group A of formula (I) -(VI) are known and may be prepared according to WO 99/03984, (Ciba) EP-A-O 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:
  • halogen derivatives transition metal such as for example Cu or Cu(I) salt, for example CuCI or CuBr
  • 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).
  • halogen derivatives can be easily prepared by well-known organic reactions, for example acylation of the corresponding alcohols or amines with suitable haloacid derivatives.
  • Example 1 Preparation of ⁇ ,o-Poly-(n-butyl acrylate)-co-(polysiloxane) [A-B-A structure]
  • the hydrosilylation is carried out to a residual SiH-value ⁇ 0,02 mmol/g.
  • Xylene is removed by distillation under reduced pressure.
  • 50 g (390 mmol) of n-butyl acrylate is added.
  • the mixture is degassed twice, heated to 130 °C and polymerization is carried out to a solid content of ⁇ 50 %.
  • the remaining volatiles (-44,5 g) are removed by distillation under vacuum. 44,5 g of a clear yellowish viscous fluid is obtained.
  • the residual SiH content is reacted away by addition of octene.
  • the hydrosilylation is carried out to a residual SiH-value ⁇ 0,02 mmol/g.
  • Xylene/octene is removed by distillation under reduced pressure.
  • 80 g (624 mmol) of n-butyl acrylate is added.
  • the mixture is degassed twice, heated to 130 °C and polymerization is carried out to a solid content of ⁇ 50 %.
  • the remaining volatiles ( ⁇ 45 g) are removed by distillation under vacuum. 44,5 g of a clear yellowish viscous fluid is obtained.
  • Positions 1 to 3 are agitated homogeneously by spatula.
  • Positions 1 to 3 are agitated to a homogeneous mixture.

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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(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 (1) or (2).

Description

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)
(I) under hydrosilylation conditions. Polymers containing e.g. poly-styrol-
Figure imgf000002_0001
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)
Figure imgf000002_0002
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, Ci-Ci8-alkyl, QrCβcycloalkyl or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, CrC4alkoxy, CrC4alkylthio, Ci-C4alkylamino or di(Ci-C4alkyl)amino;
R3, R4 and R5 independently of one another are hydrogen or d-Ci8alkyl or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring;
R6 is hydrogen or CrCi8alkyl or phenyl; X is O, NH or NR7, wherein R7 is Ci-Ciβalkyl, C3-Cβcycloalkyl or phenyl; Y is a direct bond, CrC30alkylene or C6-Ci2arylene, with the proviso that the compound of formula I is not
Figure imgf000003_0001
or
Another aspect of the invention is a polysiloxane modified initiator/regulator of the formula
Figure imgf000003_0002
Figure imgf000003_0003
wherein
A, R1, R2, R3, R4, R5, Re, 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 (Ia), (Ma) or (lib) b) reacting the resulting alkoxyamine functional polysiloxane (Ia), (Ma) or (Mb) 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 (Vl)
Figure imgf000004_0001
Figure imgf000004_0002
under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (IMa) , (IVa or IVb), (Va), (Via or VIb)
Figure imgf000004_0003
- A -
Figure imgf000005_0001
wherein A, R1, R2, R3, R4, R5, Re X and Y, W, a are as defined above under formula (I) c) reacting the resulting alkoxyamine functional polysiloxane with at least one vinylic monomer 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 Ia 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 (Ia), 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 (CrC22)alkyl esters, acrylic acid (C1-C22)- hydroxyalkyl esters, methacrylic acid (CrC22)alkyl esters, methacrylic acid (C-ι-C22)hydroxy- alkyl esters, acrylic acid (CrC22)alkyl esters or methacrylic acid (CrC22)alkyl esters which are substituted by amino, (Ci-C22)alkylamino, (Ci-C22)dialkylamino, -SO3H, epoxy, fluoro, perfluoro or siloxane groups, styrene, substituted styrene, acrylamide and methacrylamide, N-mono(Ci-C22)alkyl acrylamide, N,N-di(CrC22)alkyl acrylamide; provided that the amount of unsubstituted acrylic acid (CrC22)alkyl esters or/and methacrylic acid (CrC22)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)- acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl- (meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide 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 (CrC22)alkyl esters or methacrylic acid (CrC22)alkyl esters which are substituted by amino, (Ci-C22)alkylamino, (Ci-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)2Si0i/2 wherein R is CrC6alkyl 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.
Preferred examples are:
Me Me Me
Me
\ / Me— Si. l> Si. -, Si-H
Me ° ° Me monofunctional
Figure imgf000007_0001
difunctjona|
Mee
Figure imgf000007_0002
multifunctional distributed
Figure imgf000008_0001
branched H-siloxane (trifunctional)
Figure imgf000008_0002
branched H-siloxane (tetrafunctional)
Me = methyl, n=1-200, x = 0-100, y = 1-100
Definitions: CrC28alkyl radicals are linear or branched 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.
Cs-Cβcycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
CrC30alkylene bridges are linear or branched and may be interrupted by at least one N or O atom. Preferred are CrC^alkylene bridges, more preferably of C2-C6alkylene bridges like ethylene, propylene, butylene, pentylene, hexylene.
C2-Ci2alkylene bridges interrupted by at least one N or O atom are, for example, -CH2-O-CH2-CH2, -CH2-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-CH2-, -CH2-NH-CH2-CH2-NH-C^- or -CH2-N H-CH2-CH2-O-CH2-.
C6-C"i2arylene is, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
Preferably Ri and R2 are hydrogen or d-C4alkyl, more preferably hydrogen or methyl. Preferably R3, R4 and R5 are hydrogen or d-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)
Figure imgf000009_0001
wherein Gi, G2, G3, G4 are independently CrC6alkyl or Gi and G2 or G3 and G4, or Gi and G2 and G3 and G4 together form a C5-Ci2cycloalkyl group;
G5, G6 independently are H, CrCi8alkyl, phenyl, naphthyl or a group COOCrCi8alkyl;
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 (I) or (II); or (Ia), (Na) or (Mb) is a compound wherein
R1 and R2 independently of one another are hydrogen or Ci-Ci8-alkyl,
R3, R4 and R5 independently of one another are hydrogen or d-Ciβalkyl;
R6 is hydrogen or CrCi8alkyl; X is O, NH or NR7, wherein R7 is CrCi8alkyl,
Y is a direct bond or CrC30alkylene
A is a residue of formula A, B or O,
Figure imgf000010_0001
wherein
R8 is hydrogen, d-Ci8alkyl 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 α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
Rg is CrCiealkyl, C5-C7cycloalkyl, C2-Cealkenyl 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 Ci-Ci2alkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-Ci8alkanoyl, C3-C5alkenoyl or benzoyl;
Gi and G3 are methyl and G2 and G4 are ethyl or propyl or d and G2 are methyl and G3 and
G4 are ethyl or propyl; G5 is hydrogen or CrC4alkyl.
Especially preferred is a compound of the formula (I) or (II) or of the formula (Ia), (Na) or (lib) wherein Ri and R2 independently of one another are hydrogen or Ci-Ci8-alkyl,
R3, R4 and R5 is hydrogen,
R6 is hydrogen,
X is O,
Y is CrC30alkylene A is a residue of formula O,
Figure imgf000010_0002
wherein Gi and G3 are methyl and G2 and G4 are ethyl or propyl or d and G2 are methyl and G3 and
G4 are ethyl or propyl;
G5 is hydrogen or d-C4alkyl.
The above compounds and their preparation are described in GB 2 335 190 and GB 2 361 235 and in US6,353,107.
Another preferred structural element of formula (X) are those of formula (Xa), (Xb), (Xc), (Xd), (Xe) or (Xf)
Figure imgf000011_0001
wherein R2oi, R202, R203 and R204 independently of each other are CrCi8alkyl, C3-Ci8alkenyl, C3-Ci8alkinyl, CrCi8alkyl, C3-Ci8alkenyl, C3-Ci8alkinyl which are substituted by OH, halogen or a group -0-C(O)-R2Os, C2-Ci8alkyl which is interrupted by at least one O atom and/or NR20S group, C3-Ci2cycloalkyl or C6-Ci0aryl or R201 and R202 and/or R203 and R204 together with the linking carbon atom form a C3-Ci2cycloalkyl radical; R205, R206 and R207 independently are hydrogen, Ci-Ci8alkyl or C6-Ci0aryl; R208 is hydrogen, OH, Ci-Ci8alkyl, C3-Ci8alkenyl, C3-Ci8alkinyl, Ci-Ci8alkyl, C3-Ci8alkenyl, C3- Ci8alkinyl which are substituted by one or more OH, halogen or a group -0-C(O)-R205, C2- Ci8alkyl which is interrupted by at least one O atom and/or NR205 group, C3-Ci2cycloalkyl or C6-Ci0aryl, C7-C9phenylalkyl, C5-Ci0heteroaryl, -C(O)-CrCi8alkyl, -O-CrCi8alkyl or -COOCr Ci8alkyl; R209, R210, R211 and R2-I2 are independently hydrogen, phenyl or Ci-Ci8alkyl. More preferably in formula (Xa), (Xb), (Xc), (Xd), (Xe) and (Xf) at least two of R2oi, 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 (Xl)
Figure imgf000012_0001
(Xl) wherein
G11, G12, G13 and G14 are independently CrC4alkyl or G11 and G12 together and G13 and G14 together, or G11 and G12 together or G13 and G14 together are pentamethylene; G15 and G16 are each independently of the other hydrogen or Ci-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, CrC18alkyl or phenyl;
if k is 1 R301 is H, straight or branched CrC18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C-ι-C8alkoxy, carboxy, C-ι-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl; phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more CrC8alkyl, halogen, OH, CrC8alkoxy, carboxy, C-ι-C8alkoxycarbonyl; -C(O)-C-ι-C36alkyl, or an acyl moiety of a α,β-unsatu rated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
-SO3O+, -PO(O"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 R3oi is CrCi8alkylene, C3-Ci8alkenylene or C3-Ci8alkinylene, which may be unsubstituted or substituted, by one or more OH, d-Cβalkoxy, carboxy, C-i-Cβalkoxycarbonyl; or xylylene; or
R3oi 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,
R3oi is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and if k is 4, R3oi is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
Preferably dβ is hydrogen and Gi5 is hydrogen or Ci-C4alkyl, in particular methyl, and Gii and Gi3 are methyl and Gi2 and Gi4 are ethyl or propyl or Gn and Gi2 are methyl and Gi3 and Gi4 are ethyl or propyl.
The 4 imino compounds of formula (Xl) 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 atoms.
Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butyl or hydroxy hexyl.
Examples for halogen substituted alkyl are dichloropropyl, monobromobutyl or trichlorohexyl.
C2-Ci8alkyl interrupted by at least one O atom is for example -CH2-CH2-O-CH2-CH3, -CH2- CH2-O-CH3- or -CH2-CH2-O-CH2-CH2-CH2-O-CH2-CH3-. It is preferably derived from polyethlene glycol. A general description is -((CH2)a-O)t,-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
C2-Ci8alkyl 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-Ci2cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.
C6-Ci0 aryl is for example phenyl or naphthyl, but also comprised are CrC4alkyl substituted phenyl, Ci-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.
C7-C9phenylalkyl is benzyl, phenylethyl or phenylpropyl.
C5-Ci0heteroaryl is for example pyrrol, pyrazol, imidazol, 2, 4, dimethylpyrrol, 1 -methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine, α-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 β- (3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
CrCi8alkanoyl is for example, formyl, propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl and C3-C5alkenoyl is in particular acryloyl.
Particularly suitable nitroxyl radicals are those of formulae
Figure imgf000015_0001
In a very specific embodiment the nitroxyl radical is
Figure imgf000015_0002
Preparation
1. Preparation of the compounds of formula I
The nitroxyl radicals which are the precursors of the group A of formula (I) -(VI) are known and may be prepared according to WO 99/03984, (Ciba) EP-A-O 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:
Figure imgf000016_0001
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(I) 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).
Figure imgf000016_0002
X =CI, Br, J,
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 α,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 α,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 < 0,02 mmol/g. Xylene is removed by distillation under reduced pressure. 50 g (390 mmol) of n-butyl acrylate is added. The mixture is degassed twice, heated to 130 °C and polymerization is carried out to a solid content of ~ 50 %. The remaining volatiles (-44,5 g) are removed by distillation under vacuum. 44,5 g of a clear yellowish viscous fluid is obtained.
GPC: Mn= 6018 g/mol; Mw= 7798 g/mol PD = 1 ,29
Regulator A*> :
Figure imgf000017_0001
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 < 0,02 mmol/g. Xylene/octene is removed by distillation under reduced pressure. 80 g (624 mmol) of n-butyl acrylate is added. The mixture is degassed twice, heated to 130 °C and polymerization is carried out to a solid content of ~ 50 %. The remaining volatiles (~ 45 g) are removed by distillation under vacuum. 44,5 g of a clear yellowish viscous fluid is obtained.
GPC: Mn= 7775 g/mol; Mw= 11042 g/molPD = 1 ,42 Examples 3 - 10 were carried out in the same way described in Example 2.
Figure imgf000018_0001
C *: comb-like siloxanes (i.e. - [(Me)2SiO]n[MeSiHO]m-) L *: α,o-dihydrogen siloxanes (i.e. HMe2SiO[(Me)2SiO]n[Me2SiH) [Mn/Mw/PD]*: mol weight distribution/polydispersity
APPLICATION RESULTS
Anti crater performance
A Anti crater performance in 2 pack PU
1 ) Formulation 2 pack Polyurethane Table 1
Figure imgf000018_0002
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.
2) Formulations for anti crater performance tests of the siloxane modified acrylic leveling agent: Table 2
1 2 3 4
1 ) 2 pack PU (g) 74. 00 73. 63 73. 26 72. 52
2) Example 1 - 20 (g) 0 00 0. 50 1. 00 2 00
3) Desmodur N 75 (g) Polyisocyanate resin 26. 00 25. 87 25. 74 25. 48
Total 100 00 100. 00 100. 00 100 00
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 μm wire bar.
4) Results
Table 3 1 = no craters; 8 = a lot of craters.
Figure imgf000019_0001
B Slip performance in Stoving enamel
1 ) Formulation stoving enamel: Table 4
Figure imgf000020_0001
Positions 1 to 3 are agitated to a homogeneous mixture.
2) Formulations for slip performance tests of the siloxane modified acrylic leveling agent:
Table 5
Figure imgf000020_0002
3) Preparation of the draw downs:
Draw downs of 75 μm are prepared on plastic films.
The draw downs have to rest for 10 minutes before curing.
Bake out time 30 min (5)135 °C.
4) Results Coefficient of friction: Table 6
Figure imgf000021_0001
Figure imgf000021_0002

Claims

Claims
1. A compound of formula (I) or (II)
Figure imgf000022_0001
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, Ci-Ci8-alkyl, QrCβcycloalkyl or phenyl which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, CrC4alkoxy, CrC4alkylthio, Ci-C4alkylamino or di(Ci-C4alkyl)amino;
R3, R4 and R5 independently of one another are hydrogen or d-Ci8alkyl or phenyl; or R3 and R5 together with the linking group C=C form a 5 to 12 membered ring;
R6 is hydrogen or CrCi8alkyl or phenyl;
X is O, NH or NR7, wherein R7 is C-i-C-iealkyl, C3-Cβcycloalkyl or phenyl;
Y is a direct bond, CrC30alkylene or C6-Ci2arylene, with the proviso that the compound of formula I is not
Figure imgf000022_0002
2. A polysiloxane modified initiator/regulator of the formula
Figure imgf000022_0003
Figure imgf000022_0004
wherein
A, R1, R2, R3, R4, R5, Re, X and Y independently of one another are as defined in claim 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.
3. A polysiloxane modified initiator/regulator according to claim 2, wherein W is
monofunctional
Figure imgf000023_0001
difunctional
multifunctional distributed
anched H-siloxane (trifunctional)
Figure imgf000023_0002
branched H-siloxane (tetrafunctional)
Me = methyl, n=1-200, x = 0-100, y = 1-100
4. A compound of the formula (I) or (II) of claim 1 or the formula (Ia), (Ma) or (lib) of claim 2 wherein
R1 and R2 independently of one another are hydrogen or Ci-C18-alkyl,
R3, R4 and R5 independently of one another are hydrogen or d-Ciβalkyl; R6 is hydrogen or d-Ci8alkyl;
X is O, NH or NR7, wherein R7 is CrC iβalkyl,
Y is a direct bond or Ci-C3oalkylene
A is a residue of formula A, B or O,
Figure imgf000024_0001
wherein
R8 is hydrogen, CrCi8alkyl 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 α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
R9 is Ci-Ci8alkyl, 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 CrCi2alkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-Ci8alkanoyl, C3-C5alkenoyl or benzoyl;
Gi and G3 are methyl and G2 and G4 are ethyl or propyl or d and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or CrC4alkyl.
5. A compound of the formula (I) or (II) of claim 1 or of the formula (Ia), (Ma) or (Mb) of claim 2 wherein
R1 and R2 independently of one another are hydrogen or Ci-Ci8-alkyl,
R3, R4 and R5 is hydrogen,
Re is hydrogen,
X is O,
Y is CrC3oalkylene,
A is a residue of formula O
Figure imgf000025_0001
wherein
Gi and G3 are methyl and G2 and G4 are ethyl or propyl or d and G2 are methyl and G3 and G4 are ethyl or propyl; G5 is hydrogen or d-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 (I) or (II) as defined in claim 1 under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes (Ia), (Ma) or (Mb) as defined in claim 2, b) reacting the resulting alkoxyamine functional polysiloxane polysiloxanes (Ia), (Ma) or (Mb) 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 (Vl)
Figure imgf000026_0001
Figure imgf000026_0002
under hydrosilylation conditions to obtain alkoxyamine functional polysiloxanes Ia) , (IVa or IVb), (Va), (Via or VIb)
Figure imgf000026_0003
Figure imgf000026_0004
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.
PCT/EP2006/067410 2005-10-26 2006-10-16 Novel alkoxyamines containing unsaturated groups WO2007048719A1 (en)

Priority Applications (5)

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US12/084,022 US7812100B2 (en) 2005-10-26 2006-10-16 Alkoxyamines containing unsaturated groups
JP2008537050A JP5205270B2 (en) 2005-10-26 2006-10-16 Novel unsaturated group-containing alkoxyamines
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1288247A1 (en) * 2000-05-24 2003-03-05 Kaneka Corporation Curable compositions and compatibilizing agent
WO2004029156A1 (en) 2002-09-26 2004-04-08 Ciba Specialty Chemicals Holding Inc. Thermoplastic compositions with enhanced melt flow and compatibility
US20050065119A1 (en) * 2003-04-01 2005-03-24 Jean-Luc Couturier Alkoxyamines derived from beta-phosphorylated nitroxides, and use thereof for preparing polymerized or non-polymerized mono-or polyalkoxyamines

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6936670B2 (en) * 2001-07-05 2005-08-30 Ciba Specialty Chemical Corp. Multifunctional alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinones and their use as polymerization regulators/initiators
JP4024669B2 (en) * 2002-12-24 2007-12-19 株式会社カネカ Stabilization method of vinyl polymer having terminal group with polymerizable carbon-carbon double bond
EP1749032B1 (en) * 2004-05-27 2008-02-27 Ciba Specialty Chemicals Holding Inc. Alkoxyamines containing a radically polymerizable group

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1288247A1 (en) * 2000-05-24 2003-03-05 Kaneka Corporation Curable compositions and compatibilizing agent
WO2004029156A1 (en) 2002-09-26 2004-04-08 Ciba Specialty Chemicals Holding Inc. Thermoplastic compositions with enhanced melt flow and compatibility
US20050065119A1 (en) * 2003-04-01 2005-03-24 Jean-Luc Couturier Alkoxyamines derived from beta-phosphorylated nitroxides, and use thereof for preparing polymerized or non-polymerized mono-or polyalkoxyamines

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEM. COMMUN., 2004, pages 174 - 175
WETTER, CHRISTIAN; STUDER, ARMIDO: "Microwave-assisted free radical chemistry using the persistent radical effect", CHEM. COMMUN., 2004, Cambridge, UK, pages 174 - 175, XP009060989 *

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