MXPA01002252A

MXPA01002252A - Grafting of ethylenically unsaturated monomers onto polymers

Info

Publication number: MXPA01002252A
Application number: MXPA/A/2001/002252A
Authority: MX
Inventors: Michael Roth; Rudolf Pfaendner
Original assignee: Ciba Specialty Chemicals Holding Inc; Rudolf Pfaendner; Michael Roth
Priority date: 1998-09-03
Filing date: 2001-03-02
Publication date: 2001-09-07

Abstract

The present invention relates to a process for the preparation of grafted polymers wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a stable nitroxyl radical (NO•);and in a second step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer to a temperature at which cleavage of the nitroxyl-polymer bond occurs and polymerization of the ethylenically unsaturated monomer or oligomer is initiated at the polymer radical;maintaining said temperature for further polymerization and afterwards cooling down the mixture to a temperature below 60°C. Further subjects are grafted polymers prepared by said process, the use of the polymeric radical initiator and the use of NO radicals for grafting polymers.

Description

GRAFTING OF EFFECTIVELY UNSATURATED MONOMERS ON POLYMERS FIELD OF THE INVENTION The present invention relates to a process for the preparation of grafted polymers, wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which comprises heating a polymer and a compound containing a radical NO * stable above the melting point of the polymer, mixing and reacting the components at such a temperature; and in a second step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer at a temperature at which cleavage of the nitroxyl-polymer linkage occurs. Additional objects of the present invention are grafted polymers separated by such a process, the use of the initiator of the polymeric radical and the use of a NO stable radical for grafting polymers.

BACKGROUND OF THE INVENTION The increase in activities has been directed towards the chemical modifications of existing polymers to obtain novel functional and / or designed materials. The chemical modifications of existing polymers are important for at least two reasons: 1. It can be a cheap and fast way to obtain new polymers without having to look for new monomers; 2. They may be the only way to synthesize polymers with the new intended characteristics. An important chemical modification is the free radical grafting of reactive monomers, which involves the reaction of a polymer with a monomer or monomer mixture containing a vinyl group capable of forming grafts on the polymer backbone. If the grafts are long, the modified polymer becomes a true grafted copolymer, of which the properties will be very different from those of the original polymeric substrate. When the grafts are short, with less than, say, five portions, most of the physical or mechanical properties of the modified polymer substrate will be retained. The properties are further influenced by the structure of the grafted monomer. For example, the grafting of a polar monomer onto a non-polar polymer such as polyethylene results in decisively modified properties such as adhesion to other substrates, compatibility with polar surfaces, even at short chain lengths. The advantages of free radical grafting are also gained with the use of batch mixers or screw extruders as chemical reactors, which allows the graft reaction by free radicals to occur without solvents. This is described for example by G. H. Hu et al., In "Reagent Modifiers for Polymers", first edition, Blackie Academic & Professional a Chapman Print & Hall, London 1997, chapter 1, pages 1-97. These graft reactions by free radicals are usually carried out in the presence of a source of free radicals such as a peroxide and a reactive monomer, such as for example acrylic acid. However, the use of free radical sources such as peroxides can cause undesirable properties and lead to problems during processing (gel formation, cross-linking, molecular weight reduction) or during use. Typically the long-term stability is reduced and / or the polymer can no longer be used in outdoor applications or applications at elevated temperatures. EP-A-621 878 describes a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligomeric homopolymers and copolymers, including block and graft copolymers. The process employs a stable free radical such as, for example, the formula (in part) R'R''N-0 * and a free radical initiator. !. & BRIEF DESCRIPTION OF THE INVENTION It has surprisingly now been found that with such R'R''N-0'-compounds it is possible to produce a polymeric radical initiator by grafting the R'R''N-0 group to the polymer and using this macroinitiator for additional grafting reactions of ethylenically unsaturated monomers. The polymerization processes and the resin products of the present invention are useful in many applications, including a variety of special applications, such as for the preparation of grafted block copolymers which are useful as compatibilizing agents for polymer blends, adhesion promoters or dispersing agents for coating systems. An object of the present invention is a process for the preparation of a grafted polymer where, in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a stable nitroxyl radical (NO *); and in a second step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer at a temperature at which cleavage of the nitroxyl-polymer linkage occurs and the polymerization of the ethylenically unsaturated monomer or oligomer is initiated in the polymer radical; maintain the temperature for further polymerization and then cool the mixture to a temperature below 60 ° C. The reaction mixture after step A) can also be cooled to a temperature lower than 60 ° C before the additional step reaction is carried out B. Optionally, the source of free radicals is additionally present. Preferably the source of free radicals is a bis-azo compound, a peroxide or a hydroperoxide. The sources of specific preferred radicals are 2, 2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2, -dimethylvaleronitrile), 2,2'-azobis ( 4-methoxy-2, -dimethylvaleronitrile), 1,1''-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis- (isobutyramide), 2-phenylazo-2,4-dimethyl-4-methoxivalero-nitrile , dimethyl-2, 2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2, 2 '-azobis (N, N' -dimethylenisobutyramidine), free base or hydrochloride, 2,2'-azobis (2-amid? nopropane), free base or hydrochloride, 2,2'-azobis (2-methyl-N- [ 1, 1-bis (hydroxymethyl) ethyl] propionamide. 2,2 '-azobis. { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide; acetyl cyclohexane sulfonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis (2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, peroxide didecanoyl, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, peroxide diacetyl, dibenzoyl peroxide, t-butyl per-2-ethylhexanoate, bis- (4-chlorobenzoyl) peroperoxide, t-butyl perisobutyrate, t-butyl permaleinate, 1, 1-bis (t-butylperoxy) 3, 5, 5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononatoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate , t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2, 5- di-t-butyl peroxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, a, a'- bis (t-butylperoxy isopropyl) benzene, 3,5-bis (t-butylperoxy) 3, 5-dimethyl-1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexin-2, 5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2, 4, 5-tetraoxa cyclononane, p-25 hydroperoxide, pentane hydroperoxide, mono-a-hydroperoxide . z. ... z. ., z.-y.-¿: i ^ ii (Í ^ ¿S¡, Szii - z ^ -.- i? au ..-. 7",." ...,.-.... ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ or t-butyl hydroperoxide The peroxides are the most preferred Examples of suitable polymers are those mentioned below: 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent -l-ene, polyisoprene or polybutadiene, as well as cycloolefin polymers, for example of cyclopentene or norbornene, polyethylene (which may be optionally crosslinked), for example high density polyethylene (HDPE), high density polyethylene and high weight molecular (HDPE- HMW), high density polyethylene and ultra-high molecular weight (HDPE-UHM), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE), and (ULDPE). The polyolefins, ie the polymers of monoolefins and employed in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods, and especially by the following: a) radical polymerization (usually under high pressure and at temperature elevated). b) catalytic polymerization using a catalyst that normally contains one or more than one of the , - »_ # í5f3 • = ^ te ^ ¡.- ^ 7 ^^ Yes-. fey?, Bfe.ti ^^ A7 metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls which may be either p- or s-coordinated. These metal complexes can be in free form or fixed on substrates, typically on magnesium chloride, titanium (III) chloride, alumina or activated silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or additional activators can be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being the elements of the groups , lia and / or Illa of the Periodic Table. The activators can be conveniently modified with additional ester, ether, amine or silyl ether groups. These catalyst systems are usually called Phillips catalysts, Standard Oil Indiana, from Ziegler (-Natta), TNZ (DuPont), metallocene or single-site catalysts (SSC). 2. The polymer mixtures mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of the different types of polyethylene (for example LDPE / HDPE). 3. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butyl copolymers 1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and blends of such copolymers with others and with the polymers mentioned in 1) above, for example copolymers of polypropylene / ethylene-propylene, copolymers of LDPE / ethylene vinyl acetate (EVA), copolymers of LDPE / ethylene acrylic acid (EAA) , LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides. 4. Hydrocarbon resins (eg C5-C9) including hydrogenated modifications thereof (eg adhesives) and mixtures of polyalkylenes and starch. 5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl methacrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of styrene copolymers of high impact strength and other polymers, for example a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene. 7. The grafted copolymers of styrene or α-methylstyrene, for example copolymers of styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, ^^^^^^^^ g ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ g ^^^^^^^ acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example copolymer mixtures known as ABS, MBS, ASA or polymers. AES 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo and copolymers of epichlorohydrin, especially polymers of compounds of vinyl-containing halogen, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate copolymers or vinylidene chloride / vinyl acetate. 9. Polymers derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified by impact with butyl acrylate. 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example copolymers of acrylonitrile / butadiene, copolymers of acrylonitrile / alkyl acrylate, copolymers of acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide or terpolymers of acrylonitrile / alkyl methacrylate / butadiene. 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl or polyallyl phthalate. melamine; as well as their copolymers with the olefins mentioned in 1) above. 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide such as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulphides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof. 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acids and with or without an elastomer as a modifier, for example poly-2, 4, 4, -trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the polyamides mentioned above with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles. 18. Polyesters derived from dicarboxylic acids and / or hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from polyethers finished in hydroxyl; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates. 20. Polysulfones, polyether sulfones and polyether ketones. 21. Mixtures of the polymers mentioned above (polyblends), for example PP / EPDM, Polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR, PC / PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO , PBT / PC / ABS or PBT / PET / PC. Preferred polymers are polyethylene, polypropylene, polystyrene, block copolymers of styrene, polybutadiene or polyisoprene, EPDM (ethylene-propylene diene monomer) or EPR (ethylene-propylene rubber).

Most preferred are polyethylene, polypropylene, polybutadiene, SBS and EPDM (ethylene-propylenediene monomer). A preferred nitroxyl radical is that of formula (X) where is not 0 or 1 Rioic Rio? Ri03 are each independently of one another hydrogen, halogen, N02, cyano, -CONR105R106, - (R109) COOR? 0, -C (0) -R? O7, -ORios, -SRios, -NHR108, -N (R10β) 2f carbamoyl, di (Ci-Cis alkyl) carbamoyl, -C (= NR) (NHRiod); unsubstituted Ci-Ciβ alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 7 -C 9 phenylalkyl, C 3 -Cy 2 cycloalkyl or C 3 -C 7 cycloalkyl containing at least one C 3 -C 8 alkynyl nitrogen or oxygen; or C 1 -C 8 alkyl, C 2 -C 8 alkenyl, alkynyl C2-C? S, C7-C9 phenylalkyl, C3-C12 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy? , C? -C4 alkoxy, : Mé¿á? ^^? ? < RTI ID = 0.0 > C < / RTI > alkyl, C 1 -C 4 alkylamino or di (C 4 -C 4 alkyl) amino; or phenyl, which is or is not substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino or di (C 1 alkyl). ~ C4) amino; or R102 and RIO3? together with the bonding carbon atom, they form a cycloalkyl radical of C 3 -C 2, a radical (C 4 -C 2 cycloalkanon) -yl or a cycloalkyl radical of C 3 -Ci 2 radical containing at least one O and / or a group NR? o8; or if it is not 1 R? O is hydrogen, C? -C? 8 alkyl, phenyl, an alkali metal cation or a tetraalkylammonium cation; R105 and Rioß are hydrogen, Ci-Cis alkyl, C-Ci8 alkyl which is substituted by at least one hydroxy group or, taken together, form a C2-C12 alkylene bridge or an alkylene bridge of C2-C 2 interrupted by at least one O and / or NRioß atom; R107 is hydrogen, C? -C? 8 alkyl or phenyl; Ríos is hydrogen, Ci-Cis alkyl or C 2 -C 8 alkyl which is substituted by at least one hydroxy group; R109 is C? -C? 2 alkylene or a direct bond; ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ RuO is alkyl of C4-C? 8 attached via a tertiary C-atom to nitrogen atom, phenylalkyl of Cg-Cn, cycloalkyl of C3-C? 2 or cycloalkyl of C-C? 2 containing at least one nitrogen or oxygen atom; or C 4 -C 4 alkyl linked via a tertiary C atom to the nitrogen atom, C 9 -C 11 phenylalkyl, C 3 -Cy 2 cycloalkyl or C 3 -C 2 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; or phenyl, naphthyl, which are or are not substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino or di (C 1 alkyl) -C4) amino; if nx is 1 Rui is Ci-Cis alkyl, C7-C9 phenylalkyl, C3-C12 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom; or Ci-Cis alkyl, C7-C9 phenylalkyl, C3-C12 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino or di (C alkyl? ~ C4) amino; or a polycyclic cycloaliphatic ring system or a cycloaliphatic polycyclic ring system with at least one di or trivalent nitrogen atom; or R110 and Pin together form a C2-C2 alkylene bridge, a C3-C12 alkylene bridge or a C2-C2 alkylene bridge which is interrupted by at least one O or N atom, bridges which are unsubstituted or substituted by C 1 -Cis alkyl, hydroxy (C 1 -C 4) alkyl, phenyl, C 7 -C 9 phenylalkyl, NO 2, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, alkylthio C1-C4, C1-C4 alkylamino or di (C C4 ~ 5?) amino, R112 is hydrogen, - (R 09?) COOR 0, cyano, -OR 08,? -SR, -NHRios, -N (R? 08) 2, -NH-C (O) -Ríos, unsubstituted Ci-Cis alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenylalkyl of C7-C9, C3-C2 cycloalkyl or 0 C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom; or C? -C? 8 alkyl, C2-C? 8 alkenyl, C2_Ci8 alkynyl, C7-C9 phenylalkyl, C3-C12 cycloalkyl or C3-C? 2 cycloalkyl containing at least one nitrogen atom or oxygen, which are replaced by NO2, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl), C4) amino; or Rui and R112 together with the bonding carbon atom form a cycloalkyl radical of C3-C? 2. Another preferred nitroxyl radical is of formula XXa, XXb or XXc where Yi is 0 or CH2; Q is 0 or NR22o, where R220 is hydrogen or alkyl of R201 is C4-C? Tertiary alkyl or phenyl, which are or are not substituted by halogen, OH, C00R22? or C (0) -R222 wherein R221 is hydrogen, an alkali metal atom or C? -C? 8 alkyl and R222 is C? -C? 8 alkyl; or .- r.¡l ^ -Í ^ ^^^^ .....: ^ - y¡ítz¿Íá ... ^, •. .

R2o? it is C5-C12 cycloalkyl, C5-C12 cycloalkyl which is interrupted by at least one 0 or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical which is interrupted by at least one 0 or N atom; R202 and R2O3 with independently alkyl of C? -C? 8, benzyl, C5-C12 cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, C00R22? or C (0) -R222 or together with the carbon atom form a cycloalkyl ring of C5 ~ 2; if Yi is 0, R204 and R212 are OH, 0 (alkali metal) alkoxy C? ~ C? 8, benzyloxy, NR223R224, where R223 and R224 are independently of each other hydrogen, C? -C? 8 alkyl or phenyl, which are or are not substituted by halogen, OH, COOR221 or C (0) - R222; if Yi is CH2, R204 is OH, C? -C? 8 alkoxy, benzyloxy, OC (O) -alkyl (C? -C? 8) or NR223R224 R212 are a group C (0) R225r where R225 is OH , C? -C? 8 alkoxy, benzyloxy, NR223R224, where R223 and R224 are independently from each other hydrogen, C? -C? 8 alkyl or phenyl, which are or are not substituted by halogen, OH, COOR221 or C (0) -R222; R205, R206, R207 and R208 are independently from each other C? -C? 8 alkyl, C5-C12 cycloalkyl or phenyl; or In addition, R205 and R206 and / or R207 and R20 together with the carbon atom form a cycloalkyl ring of Cs-C2; R209 and R210 are independently hydrogen, formyl, C2-alkylcarbonyl -C? 8, benzoyl, C? -C? 8 alkyl, C5-C12 cycloalkyl, C5-C12 cycloalkyl which is interrupted by at least one 0 or N, benzyl or phenyl atom which are or are not substituted by halogen, OH, COOR22? or C (0) -R22; R2u, is formyl, C2-C? 8 alkylcarbonyl, benzoyl, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkyl which is interrupted by at least one O or N, benzyl or phenyl atom which are or are not substituted by halogen, OH , COOR221 or C (0) -R222. Another still preferred nitroxyl radical contains a structural element of formula (XXX) Gi, G2, G3, G4 are independently alkyl of CI-CT or Gi and G2 or G3 and G, or Gi and G2 and G3 and G4 together form a C5-C12 cycloalkyl group; 20 G5, G6 independently are H, C? -C? 8 alkyl, phenyl, naphthyl or a COOalkyl group of C? -C? 8. = ^^^^^^^^^^^ e ^ - ^^^^^^? ^^^^^^ The most preferred is a nitroxyl radical, where the structural element of the formula (XXX) is any of the Formulas A to S. * • * - *, 3r '- * ^ • ^ * afafc - aa ». athSyXÜry, z -y &A: z yz A .. yalS? AJK3 & Jb & (M) S & amp; £ ké where Gi, G2, G3 and G4 are independently alkyl of 1 to 4 carbon atoms, or Gi and G2 together and G3 and G4 together, or Gi and G2 together or G3 and G4 together are pentamethylene; G5 and G6 are independently hydrogen or Ci-C4 alkyl; R, if m is 1, is hydrogen, C 1 -C 8 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid which has from 2 to 18 carbon atoms, from a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, or a "S? ^ W ^ K ^ k ^. ^^ í8 < ^^^^ ~% > i ^^^^^? ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^ - ^ i ^ ^ ^ carboxylic acid a, b- does not have 3 to 5 carbon atoms or an aromatic carboxylic acid having from 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic portion by 1 to 3 groups -C00Z? 2, in which, Zi2 is H, CI-C2O alkyl? C3-C? 2 alkenyl, C5-C7 cycloalkyl, phenyl or benzyl or R is a monovalent radical of a carbamic acid or acid containing phosphorus or a monovalent silyl radical, R, if m is 2, is C 2 -C 2 alkylene, alkenylene of C4-C12, xylylene, a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid which it has 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two groups -COOZ12; or R is a divalent radical of an acid containing phosphorus or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic portion by -C00Z? 2, of an aromatic or phosphorus-containing tricarbamic acid , or is a trivalent silyl radical, R, if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; 5 p is 1, 2 or 3, R 1 is C 1 -C 12 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; when p is 1, R 2 is C 1 -C 8 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl 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 where Z is hydrogen, methyl or phenyl; or when p is 2, R 2 is C 2 -C 2 alkylene, C 6 -C 2 arylene, xylylene, a group -CH 2 CH (OH) CH 2-0 -B-0-CH 2 CH (OH) CH 2 -, where B is C2-C2 alkylene, C6-C5 arylene or C6-C2 cycloalkylene; or, provided that Ri is not alkanoyl, alkenoyl or benzoyl, R It can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or it can be a -CO- group; or Ri and R2 together when p is 1 can be a cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid; or 25 R2 is a group (sajase ¿fe_¿ &, where T7 and T8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T7 and T8 together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3, R2 is 2,4,6-triazinyl, when n is 1, R3 is C2-C8 alkylene or C4-C22 hydroxyalkylene or acyloxyalkylene, or when n is 2, R3 is (-CH2) 2C (CH2-) 2; n is 1, R4 is hydrogen, C1-C12 alkyl, C3-C5 alkenyl, C7-C9 aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C3 alkoxyalkyl, C6-C aryl? 0, glycidyl, a group of formula - (CH 2) m -COO-Q or of the formula - (CH 2) m-0-CO-Q where m is 1 or 2 and Q is C 1 -C 4 alkyl or phenyl; or when n is 2, R4 is C2-C2 alkylene, C6-C2 arylene, a group -CH2CH (OH) CH2-0-D-0-CH2CH (OH) CH2- where D is alkylene of C2-C? O, C6-C5 arylene or C6-C? 2 cycloalkylene, or a group -CH2CH (OZ?) CH2- (OCH2CH (OZ?) CH2) 2- where Zx is hydrogen, C? -C? 8, allyl, benzyl, C2 alkanoyl -C? 2 or benzoyl; R 5 is hydrogen, C 1 -C 12 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl; E is C? -C3 alkylene / the group -CH2CH (R8) -0- where R8 is hydrogen, methyl or phenyl, the group - (CH2) 3-NH- or a direct bond; R7 is C? -C? 8 alkyl, C5-C7 cycloalkyl, C7-C? Aralkyl, cyanoethyl, C6-C? Aryl, the group -CH2CH (Rs) -OH; or a group of formula or a group of formula where G is C2-C6 alkylene or C6-C12 arylene and R is as defined above; or ^^^^^^^^^^^^^ ^^^^^^^^^ aST .4 ÜI .- •% & * - vSsr.

R7 is a group -E-CO-NH-CH2-OR6; R6 is hydrogen or C? -C? 8 alkyl; The formula (F) denotes a recurring structural unit of an oligomer where T is ethylene or 1,2-propylene, or is a structural unit derived from an α-olefin copolymer with an acrylate or alkyl methacrylate; k is 2 to 100; and Rio is hydrogen, C 1 -C 12 alkyl or C 1 -C 2 alkoxy; T2 has the same meaning as R4; T3 and T4 are independently alkylene of 2 to 12 carbon atoms, or T4 is a group T5 is C2-C2 alkylene, C5-C7 cycloalkylene, C1-C4 alkylidene di (C5-C7 cycloalkylene), phenylene or phenylene (C1-C4 alkylene); T6 is -NH (CH2) a-N (CH2) b-N [(CH2) c-N-] dH where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; Ei and E2, are different, are each oxo or imino; E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, with phenyl or naphthyl substituted by chloro or by alkyl of 1 to 4 carbon atoms or phenylalkyl of 7 to 12 carbon atoms, phenylalkyl substituted by alkyl of 1 to 4 carbon atoms; E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms; or E3 and E4 together are polymethylene of 4 to 17 carbon atoms, or polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms; and Ee is a tetravalent aliphatic or aromatic radical. Additional non-heterocyclic radicals are mentioned, for example, in WO 98/30601 or WO 98/44008, which are incorporated by reference. Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. The alkyl groups can be linear or branched.

The C 3 -C 8 alkyl which is interrupted by one or more oxygen atoms is preferably derived from ethylene oxide or propylene oxide. The C3-C8alkyl interrupted by at least one 0 atom is, for example, -CH2-CH2-O-CH2-CH3, -CH2-CH2-0-CH3 or -CH2-CH2-0-CH2-CH2 -CH2-0-CH2-CH3. This is preferably derived from polyethylene glycol. A general description is - ((CH2) a-0) b-H / CH3, where a is a number from 1 to 6 and b is a number from 2 to 10. The C3-C12 alkenyl is straight or branched and for example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecenyl including its isomers. The C3-C8 alkynyl is preferably propargyl. The C5-C12 cycloalkyl is typically cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl. The cycloalkyl which is interrupted by at least one O or N atom is, for example, 2-tetrahydroiran-yl, tetrahydrofuran-yl, 1,4-dioxan-yl, pyrrolidin-yl, tetrahydrothiophen-yl, pyrazolidin-yl, imidazolidin-yl, butyrolactone-ilo, caprolactam-yl. Examples of alkali metal are lithium, sodium or potassium. The alkyl substituted by OH is typically 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl.

The alkoxy of Cf-Cis is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. The C 1 -C 8 alkyl substituted by C 1 -C 8 alkoxy, preferably by C 1 -C 4 alkoxy, in particular by methoxy or ethoxy, is typically 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl. The C 1 -C 8 alkyl substituted by di (C 1 -C) alkyl amino is preferably, for example, dimethylamino, diethylamino, 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl. The C 1 -C 8 alkyl substituted by C 1 -C 4 alkylamino is preferably, for example, methylamino, ethylamino, 2-methylaminoethyl, 2-ethylaminoethyl, 3-methylaminopropyl, 3-ethylaminopropyl, 3-butylaminopropyl and 4-methylaminopropyl. ethylaminobutyl. C 1 -C 4 alkylthio is typically thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl and thioisobutyl. The C 1 -Cis alkylcarbonyl is for example acetyl, propionyl, butyryl, pentylcarbonyl, hexylcarbonyl or dodecylcarbonyl. -tía & fí ^ k fí, i "7.taafc" '^ ^ ^^^^^^^^^^^ g ^ ^ ^ js £ ¿¿^ ^ ^ ^ ^ ^ C7-C9 phenylalkyl or C7- aralkyl C 9 is, for example, benzyl, phenylethyl, phenylpropyl, α, α-dimethylbenzyl or α-methylbenzyl. Examples of C2-C2 alkylene bridges, preferably C2-Cg alkylene bridges, are ethylene, propylene, butylene, pentylene, hexylene. The C2-C12 alkylene bridges interrupted by at least one N or 0 atom are, for example, -CH2-0-CH2-CH2, -CH2-0-CH2-CH2-CH2, -CH2-O-CH2- CH2-CH2-CH2-, -CH2-0-CH2-CH-0-CH2-, -CH2-NH-CH2-CH2, -CH2-NH-CH2-CH2-CH2, -CH2-NH-CH2-CH2-CH2-CH2-, -CH2-NH-CH2-CH2-NH-CH2- or -CH2-NH-CH2-CH2-0-CH2-. Examples for the C4-C12 cycloalkanone-ilo are cyclopentanon-yl, cyclohexanone-yl or cycloheptanon-yl. Phenyl substituted by 1, 2 or 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy is typically methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, di-t-butolphenyl, 3,5-di-t-butyl-4- methylphenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl. Examples of polycyclic cycloaliphatic ring systems are adamantane, cuban, twistane, norbornane, bicyclo [2.2.2] octane or bicyclo [3.2.1] octane. An example of a polycyclic heteroaliphatic ring system is hexaethylenetetramine (urotropin).

Examples of monocarboxylic acids having 1 to 18 carbon atoms are formic acid, acetic acid, propionic acid, phenyl acetic acid, cyclohexane carbonic acid, mono-, di- and trichloroacetic acid or mono-, di- and trifluoro acid. -acetic. Other suitable acids are benzoic acid, chlorobenzoic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, chlorobenzenesulfonic acid, trifluoromethanesulfonic acid, methylphosphonic acid or phenylphosphonic acid. Examples of a monovalent radical of a carboxylic acid are an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, cyclohexylcarboxylic acid, benzoyl or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl radical. Additional examples are derivatives of propionic acid, laurinic acid or methylethylacetic acid or the other isomers of valeric acid. Examples of a cycloaliphatic carboxylic acid are, for example, cyclohexane carboxylic acid or cyclopentane carboxylic acid. An example of an aromatic carboxylic acid is benzoic acid. Typical unsaturated carboxylic acids are acrylic acid, methacrylic acid or crotonic acid. gfc ^^ ß ^ fc & ^^ á ^^^^^? ^^^^^^^^ The examples of a monovalent silyl radical are of the formula - (C-, H23) -Si (Z ') 2Z " , in which j is an integer in the range of 2 to 5, and Z1 and Z ", independently of each other, are C1-C4 alkyl or C1-C4 alkoxy. Examples of di-, tri- and tetravalent acids are for example the malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl (3, 5-di-tert-butyl- 4-hydroxybenzyl) malonyl or bicycloheptendicarbonyl or a group of formula trimellitoyl, citryl nitrilotriacetyl, butan-1,2,3,4-tetracarboxylic acid or pyromellitic acid. Examples of a dicarbamic acid are the hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radicals. The C-C 2 alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl. & amp; &submin;;;;;;; The alkyl substituted by hydroxy, cyano, alkoxycarbonyl or carbamide may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl. Any C 2 -C 2 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene. The C4-C12 alkenylene is, for example, butenylene, pentenylene, hexenylene, heptenylene or nonenylene including its isomers. The C6-C12 arylene is, for example, o-, m- or p-phenylene, 1,4-naphthylene or, 4'-diphenylene. The C4-C22 acyloxyalkylene is, for example, 2-ethyl-2-acetoxymethylpropylene. Any of the alkoxyalkyl substituents of C-C6 are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl. The C? -C? 8 alkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.

The nitroxyl radicals of formula (X) are known and can be prepared according to WO 99/03984, EP-A-0 891 986 or WO 98/13392. Below are some typical examples.

Nitroxyl radicals of formula XXa, b and c are also known and can be prepared according to European Patent Application No. 98810741.3. Typical examples are given below.

- Nitroxyl radicals of formula XXX are also known and can be prepared according to what is described in European Patent Application No. 98810531.8.

In addition, the DE 26 21 841, US 4 '131' 599 and DE 26 30 798 for example describe the preparation of 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine and 2,6-d? Propyl-3-ethyl-2,6-dimethyl-4-oxo-piperidine, the which are intermediates for the corresponding 1-oxo compounds. Another method for the preparation of 2,2-dimethyl-6,6-d? Alkyl-4-oxopiper? Dma is described by F. Asinger, M. Thiel, H. Baltz, Monatshefte fur Chemie 88_, 464 (1957) or by J. Bobbittt et al. in J. Org. Chem. 58, 4837 (1993). Oxidation of the piperidine compound to 1-oxo-piperidine derivatives is well known in the art and is described for example by L.B. Volodarsky, V. A. Reznikov, V.I. Ovcharenko in Synthetic Chemistry of Stable Nitroxides, CRC Press, Boca Raton 1994. The tetramethylpiperidine precursors are commercially available partially or can be prepared according to known methods. For example, US 5 096 950 and all the documents cited here describe the preparation of the precursors. The oxidation process can be carried out as described above. Below are examples.

Z- á-Ste _.- Preferably Gi, G2, G3 and G4 are methyl or ethyl and G5 and Gg are hydrogen or methyl. More preferably Gx, G2, G3 and G4 are methyl and G5 and G6 are hydrogen. Another preferred group of compounds are those where Gi and G3 are ethyl and G2 and G4 are methyl, or Gi and G4 are ethyl and G2 and G3 are methyl, and one of G5 or Gg is hydrogen and the other methyl or both are hydrogen. A preferred subgroup are the compounds of the structural formula A, B, O or P, where m is 1, R is hydrogen, C? -C? 8 alkyl which is not interrupted or interrupted by one or more oxygen atoms , cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, or an α, β unsaturated carboxylic acid having of 3 to 5 carbon atoms or aromatic carboxylic acid having from 7 to 15 carbon atoms; p is 1; Ri is C 1 -C 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; R2 is C? -C? 8 alkyl, C5-C7 cycloalkyl, C2-C8 alkenyl 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 where Z is hydrogen, methyl or phenyl. Most preferred are those of structure A or B. Preferably R is hydrogen, C 1 -C 8 alkyl, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid, having from 2 to 18 carbon atoms. carbon; R 1 is C 1 -C 2 alkyl / C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; R 2 is C 1 -C 8 alkyl, glycidyl, a group of the formula -CH 2 CH (OH) -Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl.

Another preferred subgroup is where the stable nitroxyl radical is a compound of formula (X), nor is Rioi is cyano; R102 and R103 are each independently of each other Ci-C2 alkyl or unsubstituted phenyl; or R102 and R103, together with the bonding carbon atom, form a cycloalkyl radical of C5-C7; R1 is C4-C2alkyl, attached via a tertiary C atom to the nitrogen atom, phenylalkyl of Cg-Cn or phenyl; or R110 and Rui together form a C2-C6 alkylene bridge which is or is not substituted with C1-C4 alkyl; and R112 is C1-C4 alkyl. A further preferred subgroup is where the stable nitroxyl radical is a compound of formula (XXa), Y is O; R201 is tertiary C4-C8 alkyl; R202 and R203 are methyl, ethyl or together with the carbon atom form a C5-C6 cycloalkyl ring; R204 is C? -C? 8 alkoxy, benzyloxy or NR223R224, where R223 and R224 are independently from each other other hydrogen or C? -C8 alkyl; or of formula (XXb), where Qi is O; R205 'R206' R207 and R208 are independently methyl or ethyl; or R20S and R206 and / or R207 and R208 together with the carbon atom form a C5-C6 cycloalkyl ring; R209 and R210 are independently from each other another formyl, C2-C8 alkylcarbonyl, benzoyl, C? -C8 alkyl, benzyl or phenyl; or of formula (XXc), where Yi is 0; R205, R206 'R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and / or R207 and R <os together with the carbon atom form a cycloalkyl ring of C5-Cg; R211 is formyl, C2-C8 alkylcarbonyl, benzoyl, C? -C? 8 alkyl, benzyl or phenyl and R212 is OH, C? -C? 8 alkoxy, benzyloxy, NR223R224? Where R223 and R224 are independently of one another other hydrogen or C? -C? 8 alkyl. Preferably the polymer to be grafted contains unsaturated portions selected from the group consists of polydienes, styrene copolymers, random and tapered styrene block polymers, terpolymers with diolefins and copolymers with diolefins. The preferred unsaturated polymers are polybutadiene, polyisoprene, block copolymers of styrene-isoprene (SI, SIS), block copolymers ¡^ ^ J ^^^^^^^^ á ^^^ - z ^ '^? ^^^^^^ k ^^^^ í. ^^^ g ^ & ^ »^^^^ ^^ = ga¿s ^^ styrene-butadiene (SB, SBS, SEBS), ABS, EPDM, butyl rubber, chloroprene rubber and nitrile rubber having a content of unsaturated repeat units of 0.1 to 85%. Most preferred are SB, SBS, EPDM having a content of unsaturated repeat units of 1 to 70%. Preferably the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, maleic anhydride, acrolein, vinyl acetate, anhydrides of (alkyl) acrylic acid, salts of (alkyl) acrylic acid , esters (alkyl) acrylics or (alkyl) acrylamides. More preferably the ethylenically unsaturated monomer is styrene, α-methyl styrene, p-methyl styrene or a compound of formula CH 2 = C (Ra) - (C = Z) -R b, where Ra is hydrogen or C 1 -C 4 alkyl , Rb is NH2, OCH3, glycidyl, unsubstituted C? -C? Alkoxy or C? -C18 alkoxy substituted by hydroxy, unsubstituted C? ~ C? 8 alkylamino, di (C? -C? Alkyl? 8) amino, C 1 -C 8 alkylamino substituted by hydroxy or di (C 1 -C 8 alkyl) amino substituted by hydroxy; Me is a monovalent metal atom Z is oxygen or sulfur. Most preferably Ra is hydrogen or methyl, R b is NH 2, glycidyl, C 1 -C 4 alkoxy unsubstituted or substituted by hydroxy, unsubstituted C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, C 1 -C 4 alkylamino substituted by hydroxy or di (alkyl) of C? -C4) amino substituted by hydroxy; and Z is oxygen. Particularly preferred ethylenically unsaturated monomers are methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, ter. butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylates, acrylonitrile, acrylamide or methacrylamide. The temperature applied in the first reaction step depends on the polymer and is for example 50 ° to 150 ° C higher than the glass transition temperature (Tv) for amorphous polymers and from 20 ° to 180 ° C above the temperature of fusion (Tf) for semicrystalline polymers. The typical temperatures are the following: low density polyethylene LDPE 170-260 ° C high density polyethylene HDPE 180-270 ° C polypropylene PP 180-280 ° C polystyrene PS 190-280 ° C styrene block copolymers SB (S) 180-260 ° C diene ethylene-propylene modified EPDM 180-260 ° C Rubber and ethylene and propylene rubber EPR 180-260 ° C In a preferred process the temperature in the first step A) is 150 ° C to 300 ° C, more preferably 170 ° C to 280 ° C. Preferably the temperature in the second step B) is 70 ° C at 280 ° C, more preferably from 70 ° to 210 ° C. Preferably the stable nitroxyl radical is present in an amount of 0.1% to 30%, more preferably in an amount of 0.1% to 20% and more preferably in an amount of 0.5% to 10% based on the weight of polymer. Preferably, the weight ratio of the reaction product from step A) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1: 1000 to 10: 1, more preferably from 1: 100 to 1: 1 and more preferably from 1:50 to 1: 1. Step A) of the process can be carried out in any suitable reactor for mixing a molten polymer. Preferably the reactor is an extruder or kneading apparatus, as described for example in "Handbuch der Kunststoffextrusion" Vol. I, editor F. Hensen, W. Knappe and H. Potente, 1989, pages 3-7. If an extruder is used the process can be described as an extrusion process reagent. Examples of equipment and reactive extrusion processes are given by G. H. Hu et al., In "Reagent Modifiers for Polymers", first edition, Blackie Academic & Professional an Imprint by Chapman & Hall, London 1997, chapter 1, pages 1-97. Preferably, if an extruder is used, a reduced pressure is applied to less than 200 mbar during extrusion. The volatile by-products can therefore be removed. The reaction time for step A) depends on the desired amount of grafted ONR'R "initiator portions. Typical reaction times are from a few minutes to an hour. Preferably, the reaction time is from 1 minute to 1 hour, more preferably from 2 minutes to 20 minutes. Reaction step B) can be carried out immediately after step A), however it is also possible to store the intermediate polymer radical initiator at room temperature for some time. The initiator of the intermediate polymer radical is stable at room temperature and activity loss occurs for several months. Reaction step B) can be carried out in any suitable reactor for mixing a molten polymer with a monomer. It is also possible to dissolve or disperse the * Z £ g &z ~ ¿£ * .z .z polymer and add the monomer "to the solution, process B) can thus be optionally carried out in solution.The degree of grafting depends on the reaction time, the The reaction time for step B) is preferably from 1 minute to 20 hours, more preferably from 30 minutes to 5 hours, if the reaction step B) is carried out in the same manner as the polymeric initiator. an extruder, a reaction time of 2 to 20 minutes is preferred The grafted polymers are useful in many applications such as compatibilizers in polymer blends or alloys, adhesion promoters between two different substrates, surface modifying agents, nucleating agents, agents of coupling between the filler and the polymeric matrix or dispersing agents The process is particularly useful for the preparation of grafted block copolymers. they are, for example, block copolymers grafted from polystyrene and polyacrylate (for example, poly (styrene-co-acrylate) or poly (styrene-co-acrylate-co-styrene). They are useful as adhesives or as compatibilizers for polymer blends or as polymer reinforcing agents. Two-block copolymers of poly (methyl methacrylate-co-5-acrylate) or three-block copolymers of poly (methyl-co-acrylate-co-methacrylate acrylate) are useful as dispersing agents for coating systems, as coating additives (e.g. rheological agents, co-builders, reactive diluents) or as a resinous component in coatings (e.g., highly solid paints). The grafted block copolymers of styrene (meth) acrylates and / or acrylonitrile are useful for plastics, elastomers and adhesives. In addition, the grafted block copolymers of this invention, wherein the grafted blocks have polar monomers on a non-polar polymer are useful in many applications as amphiphilic or dispersing surfactants to prepare highly uniform polymer blends. Thus, the present invention also encompasses the synthesis of grafted, multi-block, stellate, gradient, random, hyperbranched, and dendritic block copolymers. The polymers prepared by the present invention are particularly useful for the following applications: adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, crosslinkers , for the treatment of paper, water treatment, electronic materials, paints, coatings, photography, materials for inks, materials for forming images, superabsorbents, cosmetics, hair products, condoms, biocide materials or asphalt modifiers, leather, textiles , ceramics and wood. Because the graft polymerization herein is a "living" polymerization, it can be initiated and stopped practically at will. In addition, the polymeric product retains the functional alkoxy amine group that allows a continuation of the polymerization in living matter. Thus, in one embodiment of this invention, once the first monomer is consumed in the initial polymerization step, a second monomer can be added to form a second block on the growing grafted polymer chain in a second polymerization step. Therefore it is possible to carry out additional graft polymerizations with some or different monomers to prepare multi-block grafted copolymers. In addition, since this is a living radical polymerization, the graft blocks can be prepared essentially in any order. Accordingly, the additional objects of the present invention are a polymeric radical initiator prepared according to step A) of the process without an additional source of free radicals and a polymeric radical initiator prepared according to step A) of the process with an additional free radical source. The initiator of the polymer radical obtainable by step A) of the above process is represented schematically in the formula (Pl) (Pl), where R498 is hydrogen, substituted or unsubstituted C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl; C3-C20 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy , cyano, carboxy; C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino, 0 (C 1 -C 8 alkyl), O (C 2 -C 8 alkenyl) , C7-Cn phenylalkyl, 0-phenyl, C7-C9 okenylalkyl or halogen or phenyl and naphthyl which are unsubstituted or substituted by C1-C4 alkyl, C1-C4 alkoxy, C? -C4 alkylthio, halogen , cyano, hydroxy, carboxy, C 1 -C 4 alkylam or di (C 1 -C 4 alkyl) amino; R499 is the stable nitroxyl radical, attached to the oxygen atom; R500 is substituted or unsubstituted C? -C? 8 alkyl, C2-C? 8 alkenyl, C3-C20 cycloalkyl, phenyl, C7-Cn phenylalkyl; R501 is hydrogen, unsubstituted or substituted C? -C? 8 alkyl, C2-C? 8 alkenyl, C2-C? Alkynyl, C3-C20 cycloalkyl 'phenyl, 0 (C? -C? 8), 0 (C2-C18 alkenyl), phenylalkyl of C7-Cn, 0-phenyl, 0-phenylalkyl of C7-C9 or halogen, CN, COOR500, CONR500R500; Qs is CR502R503 'CH = CH2, (CR502R503) n »CR504 = CR505_ CR50 R507, (CR504 = CR505 ~ CR506R507) n, C = CRs? 8R509 / (C = CRs? 8R509) n, O, C = 0, NR510, NR5n-C = 0, 0-C (0) -0, S02, S, SIR512R513, O-SIR512R513-O; R502, R503 'R504, 505 R506' R507, R508 'R509' R51O 'R51I' R512 and R513 independently of one another are hydrogen, substituted or unsubstituted Ci-Cis alkyl, C2-C? 8 alkenyl, C2 alkyl? -C? 8, C3-C7 cycloalkyl, phenyl, O (Ci-Cie alkyl), 0 (C2-C? 8 alkenyl), C7-Cn phenylalkyl, 0-phenyl, C7-C9 O-phenylalkyl or halogen; n is a number from 1 to 10; and it is a number from 1 to 25000 and; z is a number from 0 to 25000.

Preferably R50? is H or methyl; Q5 is CR502R503, CH = CH2, CR504 = CR505CR506R507, where R502 and R503 is H, methyl or C2-C9 alkenyl and R504, R505, R506 and R507 are independently H or methyl. Examples for the different substituents have already been given. Within this selection polyethylene, polypropylene, and polybutadiene, SBS and EPDM are especially preferred. A further object of the invention is a polymer of formula (P2) obtainable by step B) of the above process.

The definitions and examples of the substituents are as given above; Q6 is a homo, copolymer or taper polymer resulting from the monomers as described above, t is a number from 0 to 25000. R499 can be removed thermally or chemically.

Preferably the polymer (P2) is grafted with a monomer of the groups described above and more preferably with styrenes, (meth) acrylates, butadiene, isoprene. Most preferred are SB-g-styrenes, SB-g- (meth) acrylates, Sl-g-styrenes, Sl-g- (meth) acrylates, SBS-g-styrenes, SBS-g- (meth) acrylates, EPDM-g-styrenes, EPDM-g- (meth) acrylates. An even more object is a polymer obtainable by step A) and B) of the process as defined above. Yet another object of the present invention is a composition comprising a) a polymeric radical initiator prepared according to step A) as defined above with the preparation being optionally carried out in the presence of a source of free radicals and b) an ethylenically-based monomer or oligomer unsaturated The examples for the different substituents and their preferences have already been given, they also apply for the other objects of the invention. Additional objects are the use of a stable nitroxyl radical for the preparation of a grafted polymer as defined above and the use of a grafted polymer according to step A) as defined above., as a macronisator for radical polymerization. It is also an object of the present invention to use the polymer prepared according to the process as defined above, as an adhesive or compatibilizer for polymer blends or as agents for reinforcing polymers. The two-block copolymers of poly (methyl methacrylate-co-acrylate) or the three-block grafted copolymers of poly (methyl acrylate-co-acrylate-co-methacrylate) are useful as dispersing agents for coating systems, as additives of coating (for example rheological agents, coacerizers, reactive diluents) or as resinous components in coatings (for example, highly solid paints). The block copolymers of styrene, (meth) acrylates and / or acrylonitrile are useful for plastics, elastomers and adhesives. In addition, the grafted block copolymers of this invention, where the grafted blocks have polar monomers on a non-polar polymer are useful in many applications as surfactants or amphiphilic dispersants to prepare highly uniform polymer blends.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE INVENTION The following examples illustrate the invention.

A) Grafting of R'R''NQ * to the polymer (preparation of a polymeric initiator) In a Brabender W50 mixing chamber (40 rpm) heated to 180-220 ° C, 36.6 g of a commercially available polypropylene (MFR230) were kneaded. /2.I6 = 1-43 according to ISO 1133) under N2 for 10 min. The additives (Table 1) were introduced into the mixing chamber at the beginning, together with the polypropylene. 10 minutes later the mixing stopped. The polymeric material was removed from the mixing chamber, compression molded at 30 ° C to about 50 kN for 1 minute and crushed into granules. The granulated polymer was dissolved, precipitated again and the NMR (Nuclear Magnetic Resonance) spectra were taken at high temperature to determine if NO portions are present attached to the polymer.

Table 1 Graft of J ^ R'R '' N-O * to polypropylene compound 1: 2, 2, 6,6-tetramethyl-piperidin-l-oxyl-4-yl ester of benzoic acid compound 2: 4-hydroxy? -2,6,6-tetramethyl-piper? din- l-oxyl peroxide 1: dicumylperoxide •TO. aSkfcf. = B) Grafting of R'R''NQ * to the polymer and analogous reaction of the subsequent polymer Commercially available polymers (SBS styrene / butadiene / styrene copolymer, Kraton D 1102 CU, distributor: Shell; SEBS = styrene copolymer ethylene / butadiene / styrene Kraton G 1652, distributor: Shell, EPDM = ethylene / propylene / ethylidene norbornene terpolymer, Buna EP G, 3850, distributor: Bayer) were extruded together with the compounds given in Table 2 into a two extruder. screws (TW 100 from Haake, Germany) at 180-210 ° C (1-5 heating cycles) and 40 rpm. In an evacuated Schlenk reactor, purged with argon, 5 g of the granulated polymer was dissolved in 50-100 mL of monomer under an argon atmosphere. Dissolved oxygen will be removed in freeze-thaw cycles (liquid nitrogen) . The reaction mixture was stirred and heated under an argon atmosphere. The remaining monomer was removed under vacuum and the residue was dried under vacuum until a constant weight was reached. Molecular weights and molecular weight distribution were determined by gel permeation chromatography (GPC). The results are shown in Table 3. e Table 2 Grafting of R 'R' 'N-O * Hl polymer compound 3: 4-propoxy-2, 2,6,6-tetramethyl-piperidin-1-oxyl compound 4: (2, 2, 6, 6-tetramet? lp? peridin-l-oxyl-4-? l) ester of decandioic acid ^^^ ^^ & ^^ j ^ j & ^^^ k & * s ^^^ wS¿ ^^ compound 5: 2, ß-diethyl-2, 3, 6-trimethyl-piperidin- l-oxyl-4-yl ester of dodecanoic acid * bimodal distribution; peak molecular weight (Mp) for the high MW peak.

Table 3 Analogous reactions of the polymer * bimodal d? struc? on? peak molecular weight (Mp) for the peak MW high

Claims

REVIVENESS 1. A process for the preparation of a grafted polymer, characterized in that in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a stable nitroxyl radical (NO *); and in a second step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer at a temperature at which the cleavage of the nitroxyl-polymer bond occurs and the polymerization of the ethylenically mo- omer or oligomer unsaturated is initiated in the polymer radical; maintain the temperature for the additional polimerization and then cool the mixture to a temperature lower than 60 ° C. 2. The process according to the claim 1, characterized in that a source of free radicals is additionally present. 3. The process of compliance with the reivinpicación 2, characterized in that the free radical source s is a bis-azo compound, a peroxide or a hydroperoxide. 4. The process in accordance with the claim 3, characterized in that the source of free radicals is 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyron Ltril), 2,2'-azob? S (2, -dimethylvaleronitrile), 2,2 '-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1, 1'-azobis (1-cyclohexan-

'XJ ?? «I» »» »- J? WiJ carbonitrile), 2, 2'-azobis (isobutyramide), 2-phenylazo-2, -dimethyl-4-methoxivaleronitrile, dimethyl-2, 2'-azobisisobutyrate, 2- ( carbamoylazole) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (N, N '-dimethylenisobutyramidine), free base or hydrochloride, 2, 2'-azobis (2-amidinopropane), free base or hydrochloride, 2,2'-azobis. { 2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide} or 2, 2 '-azobis. { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide; acetyl cyclohexane sulfonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis (2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide , dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis- (4-chlorobenzoyl) peroxide, perisobutyrate of t-butyl, t-butyl permaleinate, 1,1-bis (t-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butyl peroxy isopropyl carbonate, perisononazole of t-butyl, 2,5-dibenzoate of 2,5-dimethylhexane, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, peroxide di-t-amyl, a, a'-bis (t-butylperoxy isopropyl) benzene, 3,5-bis (t-butylperoxy) 3,5-dimethyl-1,2-dioxolane, di-t-butyl peroxide , 2, 5-dimethylhexin-2, 5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinano hydroperoxide , diisopropylbenzene mono-a-hydroperoxide, eumeno hydroperoxide or t-butyl hydroperoxide. The process according to claim 1, characterized in that the polymer is polyethylene, polypropylene, polystyrene, a block copolymer of styrene, polybutadiene, polyisoprene, EPDM (ethylene-propylene diene monomer) or EPR (ethylene-propylene rubber) ). 6. The process according to claim 1, characterized in that the free nitroxyl radical is a compound of formula (X) where ni is 0 or 1 Rioi, R102, R103 are each independently of each other hydrogen, halogen, N02, cyano, -CONRiosRio, - (R109) COOR104, -C (0) -R? o7, -ORios, -SRios, • -NHRios, -N (Rivers) 2, carbamoyl, di (C? -C? Alkyl) carbamoyl, -C (= NR?) (NHRiog); unsubstituted C 1 -C 8 alkyl, C -C 8 alkenyl, C 2 -C 8 alkynyl, C 7 -C 9 phenylalkyl, C 3 -C 3 cycloalkyl or C 3 -C 7 cycloalkyl containing minus one nitrogen or oxygen atom; or C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 7 -C 9 phenylalkyl, C 3 -C 12 cycloalkyl or C 3 -C 12 cycloalkyl containing at least one carbon atom. nitrogen or oxygen, 10 which are substituted by N 0, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; or phenyl, which is or is not substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, 15 hydroxy, carboxy, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; or R102 and RIO3Í together with the bonding carbon atom, form a C3-C12 cycloalkyl radical, a radical (C4-C? 2 cycloalkanone) -yl, a cycloalkyl radical of C3-C12 radical containing at least one O-atom and / or a 20 group NR? 08; or if nx is 1
R 10
R 10 is hydrogen, C 1 -C 8 alkyl, phenyl, an alkali metal cation or a tetraalkylamino cation; Rios and Rioß are hydrogen, C? -C? 8 alkyl, C2-C? Alkyl, which is substituted by at least one hydroxy group or, taken together, form an alkylene bridge of
C2-C12 or a C2-C2 alkylene bridge interrupted by at least one atom of 0 and / or NR; R107 is hydrogen, C? -C? 8 alkyl or phenyl; Ríos is hydrogen, C 1 -C 8 alkyl or C 2 -C 18 alkyl which is substituted by at least one hydroxy group; Rog is C1-C12 alkylene or a direct bond; R 1 is C 8 -C 8 alkyl attached via a tertiary C atom to the nitrogen atom, C 9 -C n phenylalkyl, C 3 -C 12 cycloalkyl or C 3 -C 12 cycloalkyl containing at least one nitrogen or oxygen atom; or C4-C18 alkyl attached via a tertiary C atom to the nitrogen atom, phenylalkyl of Cg-Cn, cycloalkyl of C3-C12 or cycloalkyl of C3-C? 2 containing at least one atom of nitrogen or oxygen, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylamino or di (C1-C4 alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino or di (C alkyl? -C?) Am? No;
• ^^^^ A ^^^^^^^, ^ ^ Jj ^^^ á ^ ^^ a? Rui is C? -C? 8 alkyl, C7-C9 phenylalkyl, C3-C? 2 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom; or C? -C? 8 alkyl, C7-C9 phenylalkyl, C3-C12 cycloalkyl or C3-C? 2 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; or phenyl, naphthyl, which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino or di (C 1 alkyl) -C4) amino; or a polycyclic cycloaliphatic ring system or a cycloaliphatic polycyclic ring system with at least one di or trivalent nitrofen atom; or R110 and R111 together form a C2-C2 alkylene bridge, a C3-C12 alkylene bridge or a C2-C12 alkylene bridge which is interrupted by at least one O or N atom, bridges which they are unsubstituted or substituted by C 1 -C 8 alkyl, hydroxy (C 1 -C 4) alkyl, phenyl, C 7 -C 9 phenylalkyl, NO 2, halogen, amino, hydroxy, cyano, carboxy, C 1 -C 4 alkoxy, alkylthio C1-C4, C1-C4 alkylamino or di (C? ~ 25 C4 alkyl) amino,
R112 is) COOR104, cyano, -OR,
-SRioß -NHRios, "(Ríos) 2, -NH-C (O) -Ríos, unsubstituted Ci-Ciß alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 7 -C 9 phenylalkyl , C3-C12 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom, or C? -C? 8 alkyl, C2-C? 8 alkenyl, C? -Cie alkynyl, phenylalkyl C7-C9, C3-C12 cycloalkyl or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy, C1-C4 alkoxy, alkylthio of C 1 -C 4, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino, or phenyl, naphthyl, which are or are not substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 alkylthio -C4, halogen, cyano, hydroxy, carboxy, C1-C4 alkylamino, di (C1-C4 alkyl) amino, or Rui and R112 together with the bonding carbon atom form a cycloalkyl radical of C3-C? 2. The process according to claim 1, characterized in that the radica The stable nitroxyl is a compound of formula XXa, XXb or XXc Í XXb), where Yi is 0 or CH2; 5 Q is 0 or NR220 / 'where R220 is hydrogen or alkyl
C? ~ C? 8; R201 is alkyl or tertiary C4-C8 phenyl, which are or are not substituted by halogen, OH, COOR221 or C (O) -R222 where R221 is hydrogen, an alkali metal atom or C? -C alkyl Δ 8 and R222 is C? -C? 8 alkyl; or R201 is C5-C12 cycloalkyl, C5-C12 cycloalkyl which is interrupted by at least one 0 or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical which is interrupted by at least one O or N atom; R202 and R203 with independently C? -C? 8 alkyl, benzyl, C5-C12 cycloalkyl or phenyl, which are or are not substituted by halogen, OH, COOR221 or C (0) -R222 or together with the carbon form a cycloalkyl ring of C5-C? 2; 20 if Yi is 0,
^ - ^^^^ M ^^^ SÍ ^ ^ ^^: - ^ '^ ^ ¿¿di R204 and R212 are OR, - O (alkali metal) Ci-Cis alkoxy, benzyloxy, NR223R224, where R223 and R224 are independently hydrogen, C? -C? 8 alkyl or phenyl, which are or are not substituted by halogen, OH, COOR22? or C (0) -R222; if Yi is CH, R20 is OH, C? -C? 8 alkoxy, benzyloxy, 0-C (0) -alkyl (C? -C? 8) or NR223R224; R2i2 are a group C (0) R22s, where R225 is OH, C? -C? 8 alkoxy, benzyloxy, NR223R224, where R223 and R224 are independently hydrogen, C? -C? 8 alkyl or phenyl, which are or are not substituted by halogen, OH, COOR221 or C (O) -R222; R205, R206? R207 and R2o8 are independently from each other C alquilo-C? 8 alkyl, C5-C12 ciclo cycloalkyl or phenyl; or R205 and R206 and / or R207 and R208 together with the carbon atom form a cycloalkyl ring of Cs-C? 2; R209 and R210 are independently from each other hydrogen, formyl, C2-C18 alkylcarbonyl, benzoyl, C? ~C? Alquilo alkyl, C ciclo-C ciclo ciclo cycloalkyl, C5-C? Ciclo cycloalkyl which is interrupted by at least an atom of O or N, benzyl or phenyl which are or are not substituted by halogen, OH, C00R22? or C (0) -R222; R211, is formyl, C2-C? 8 alkylcarbonyl, benzoyl, C? -C18 alkyl, Cs-C? 2 cycloalkyl,
£ As .- * & • * - - C5-C? 2 cycloalkyl which is interrupted by at least one atom of 0 or N, benzyl or phenyl which are or are not substituted by halogen, OH, COOR22? or C (0) -R222. The process according to claim 1, characterized in that the stable nitroxyl radical contains a structural element of formula (XXX)
(XXX), where
Gi, G2, G3, G4 are independently Ci-C alkyl or Gi and G2 or G3 and G4, or Gi and G2 and G3 and G4 together form a cycloalkyl group of Cs-C2; G5, Ge independently are H, C? -C? 8 alkyl, phenyl, naphthyl or a COOalkyl group of Ci-Cie. 9. The process according to claim 8, characterized in that the compound containing the structural element of formula (XXX) is any of the formulas A to S
(F) ? á *? tó. * s8? 3.
(M) x d * ay «? g ^ ieiá ^ ^^ & where, j.WWaa-WBteaMask .-- .. ----- .- - Gi, G2, G3 and G4 are independently alkyl of 1 to 4 carbon atoms, or Gi and G2 together and G3 and G4 together, or Gi and G2 together or G3 and G4 together are pentamethylene; G5 and G6 are independently hydrogen or C 1 -C 4 alkyl; R, if m is 1, is hydrogen, C 1 -C 8 alkyl which is interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid that has 7 to 15 carbon atoms, or an α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms or an aromatic carboxylic acid having 7 to 15 carbon atoms, wherein each carboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic portion by 1 to 3 groups -COOZ12, in which, Z12 is H, C3-C2 alkyl C3-C12 alkenyl, C5-C7 cycloalkyl, phenyl or benzyl; or
R is a monovalent radical of a carbamic acid or acid containing phosphorus or a monovalent silyl radical; R, if m is 2, is C 2 -C 2 alkylene, alkenylene of
C4-C12, xylylene, a divalent radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid which it has 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two groups -COOZ12; or R is a divalent radical of an acid containing phosphorus or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic portion by -COOZ12, an aromatic tricarbamic acid or a phosphorus-containing acid or is a trivalent silyl radical, R, if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; p is 1, 2 or 3, R 1 is C 1 -C 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; when p is 1, R 2 is C 1 -C 8 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl 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 where
Z is hydrogen, methyl or phenyl; or when p is 2, R2 is C2-C2 alkylene, Cg-C2 arylene, xylylene, a group -CH2CH (OH) CH2-0-B-0-CH2CH (OH) CH2-, where B is C 2 -C 0 alkylene, Cg-C 5 arylene or Cg-C 2 cycloalkylene; or, provided Ri is not alkanoyl, alkenoyl or benzoyl, R 2 can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or it can be a -CO- group; or Ri and R2 together when p is 1 can be a cyclic acyl radical of an aliphatic 1,2- or 1,3-dicarboxylic acid; or R2 is a group where T7 and T8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T7 and T8 together are alkyl of 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3, R is 2,4,6-triazinyl; when n is 1, R3 is C2-C8 alkylene or hydroxy-alkylene or C4-C22 acyloxyalkylene; or when n is 2, R3 is (-CH2) 2C (CH2-) 2;
ZN when n is 1, "" * R is hydrogen, C? -C? 2 alkyl, C3-C5 alkenyl, C7-Cg aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-alkoxyalkyl Ce, C 6 -C 0 aryl, glycidyl, a group of formula - (CH 2) m - COO - Q or of the formula - (CH 2) m - 0 - CO - Q where m is 1 or 2 and Q is alkyl of C1-C4 or phenyl; or when n is 2, R4 is C2-C2 alkylene, Cd-C2 arylene, a group -CH2CH (OH) CH2-0-D-0-CH2CH (OH) CH2- where D is alkylene of C2-C? O, C6-C5 arylene or C3-C? 2 cycloalkylene, or a group -CH2CH (OZi) CH2- (0CH2CH (OZi) CH) 2- where Zx is hydrogen, C? -C? 8, allyl, benzyl, C2-C? 2 alkanoyl or benzoyl; R5 is hydrogen, C? -C? 2 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl; E is C1-C3 alkylene, the group -CH CH (R8) -0- wherein R8 is hydrogen, methyl or phenyl, the group - (CH2) 3-NH- or a direct bond; R7 is C? -C? Alkyl, C5-C7 cycloalkyl, C7-C? Aralkyl, cyanoethyl, C6-C? Aryl, the group -CH2CH (R8) -OH; or a formula group or a formula group where G is C2-C6 alkylene or Cg-C2 arylene and R is as defined above; or R7 is a group -E-C0-NH-CH2-0R6; Rg is hydrogen or C? -C? 8 alkyl; Formula (F) denotes a recurring structural unit of an oligomer where T is ethylene or 1,2-propylene, or is a structural unit derived from an α-olefin copolymer with an acrylate or alkyl methacrylate; k is 2 to 100; and Rio is hydrogen, C 1 -C 2 alkyl or C 1 -C 2 alkoxy; T2 has the same meaning as R4;
T3 and T4 are independently alkylene of 2 to 12 carbon atoms, or T4 is a group
T5 is C2-C22 alkylene, C5-C7 cycloalkylene, C? -C4 alkylidene (C5-C7 cycloalkylene), phenylene or phenylene (C? -C4 alkylene); T6 is -NH (CH2) a-N (CH2) b-N [(CH2) c-N-] dH where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; Ei and E2, being different, are each oxo or imino; E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl substituted by chloro or by alkyl of 1 to 4 carbon atoms or phenylalkyl of 7 to 12 carbon atoms or phenylalkyl substituted by alkyl from 1 to 4 carbon atoms; E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms; or E3 and E4 together are poly p-ethylene of 4 to 17 carbon atoms, or polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms; and E6 is a tetravalent aliphatic or aromatic radical. 10. The process according to claim 9, characterized in that Gi, G2 / G3 and G4 are methyl and G5 and Gg are hydrogen. 11. The process according to claim 9, characterized in that the compound is of structural formula A, B, O or P, where m is 1, R is hydrogen, C? -C? 8 alkyl which is not interrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms or an α, β unsaturated carboxylic acid having 3 to 5 carbon atoms or aromatic carboxylic acid having 7 to 15 carbon atoms; p is 1; R 1 is C 1 -C 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; - * • »feM &! DS | arf * | ^^ a ^ £ ^ Sgí¡ -a? ^ a ^ aa5- ^ afa.as = aaa ^ = - a R2 is alkyl of C? -C? 8, cycloalkyl C5-C7, alkenyl of C2-C8 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 where Z 5 is hydrogen, methyl or phenyl. 12. The process according to claim 11, characterized in that R is hydrogen, C? -C? 8 alkyl, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid; Ri is C 1 -C 2 alkyl, C 7 -C 8 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; R 2 is C 1 -C 8 alkyl, glycidyl, a group of the formula -CH 2 CH (OH) -Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl. 13. The process according to claim 6, characterized in that the stable nitroxyl radical is a compound of formula (X), nor is R101 cyano; R102 and R3O3 are each independently from each other Ci-C12 alkyl or unsubstituted phenyl; or R102 and R103, together with the bonding carbon atom, form a cycloalkyl radical of C5-C7; z¿ ^ A¿X & .. t-fafc. ~ t "A-"? ae > í «-Bt, -«.
Róo is C 4 -C 2 alkyl linked via a tertiary C atom to the nitrogen atom, C 9 -C 9 phenylalkyl or phenyl; or Ruo and Rui together form an alkylene bridge of C2-Cg which is or is not substituted with C? -C4 alkyl; and Rn2 is C1-C4 alkyl. The process according to claim 7, characterized in that the stable nitroxyl radical is a compound of formula (XXa), Y is O; R2o? is C4-C8 tertiary alkyl; R202 and R203 are methyl, ethyl or together with the carbon atom form a C5-C6 cycloalkyl ring; R204 is C? -C? 8 alkoxy, benzyloxy or NR223R224, where R223 and R224 are independently from each other other hydrogen or C? -C8 alkyl; or of formula (XXb), where Qi is O; R205, R206, R207 and R208 are independently methyl or ethyl; or R205 and R206 and / or R2o7 and R208 together with the carbon atom form a C5-C6 cycloalkyl ring; R209 and R210 are independently from each other another formyl, C2-C8 alkylcarbonyl, benzoyl, C? -C8 alkyl, benzyl or phenyl; or of formula (XXc), where Yx is O;
R205 R206 / R207 and R208 are independently methyl or ethyl; or R205 and R206 and / or R207 and R2os together with the carbon atom form a cycloalkyl ring of Cs ~ Cg; R211 is formyl, C2-C8 alkylcarbonyl, benzoyl, C? -C? 8 alkyl, benzyl or phenyl and R212 is OH, C? -C? 8 alkoxy, benzyloxy, NR223 224 where R223 and R? 24 they are independently of one another other hydrogen or C? -C? 8 alkyl. 15. The process according to claim 1, characterized in that the polymer to be grafted contains unsaturated portions selected from the group consisting of polydienes, block copolymers, random and tapering styrene, terpolymers with diolefins and copolymers with diolefins. 16. The process according to claim 1, characterized in that the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, maleic acid anhydride, acrolein, vinyl acetate, acid anhydrides. alkyl) acrylic, (alkyl) acrylic acid salts, (alkyl) acrylic esters or (alkyl) acrylamides. The process according to claim 1, characterized in that the ethylenically unsaturated monomer is styrene, α-methyl styrene, p-methyl styrene or a compound of formula CH 2 = C (Ra) - (C = Z) -Rb, where R a is hydrogen or C 1 -C 4 alkyl, R b is NH 2, OCH 3, glycidyl, unsubstituted C 1 -C 8 alkoxy or C 1 -C 8 alkoxy substituted by hydroxy, unsubstituted C 1 -C 8 alkylamino, di (C 1 -C 8 alkyl) amino, C 1 -C 8 alkylamino substituted by hydroxy or di (C 1 -C 8 alkyl) amino substituted by hydroxy; Me is a monovalent metal atom Z is oxygen or sulfur. 18. The process according to claim 17, characterized in that Ra is hydrogen or methyl, Rb is NH2, glycidyl, C1-C4 alkoxy unsubstituted or substituted by hydroxy, unsubstituted C1-C4 alkylamino, di (C1 alkyl) -C4) amino, C1-C4 alkylamino substituted by hydroxy or di (C1-C4 alkyl) amino substituted by hydroxy; and Z is oxygen. 19. The process according to claim 18, characterized in that the ethylenically unsaturated monomer is methacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylamino-ethylacrylate, glycidylacrylate, methyl (meth) acrylate, ethyl (met) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl- (meth) acrylate, glycidyl (meth) acrylates, acrylonitrile, acrylamide or methacrylamide. 20. The process according to claim 1, characterized in that the temperature in the 5 first step A) is 150 ° C to 300 ° C. 21. The process according to claim 1, characterized in that the temperature in the second step B) is from 70 ° C to 280 ° C. 22. The process according to claim 1, characterized in that the stable nitroxyl radical is present in an amount of about 0.1% to 30% based on the weight of the polymer. 23. The process according to claim 1, characterized in that the ratio of the
The reaction product from step A) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1: 1000 to 10: 1. 24. A polymeric radical initiator, characterized in that it is obtained according to step A) of
According to claim 1 or claim 2.
25. An initiator of the polymeric radicals of formula (Pl) ^^ i ^^^^ g * yg ^ |? Sg¡g Pl), characterized why R 4g 8 is hydrogen, unsubstituted or substituted C 1 -C 6 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl; C3-C2o cycloalkyl or C3-C2 cycloalkyl containing at least one nitrogen or oxygen atom or C3-C12 cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino , hydroxy, cyano, carboxy; C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino, 0 (Ci-Cis alkyl), O (C 2 -C 8 alkenyl), phenylalkyl C7-Cn, 0-phenyl, C7-C9ohalogen o-phenylalkyl or phenyl and naphthyl which are unsubstituted or substituted by C? -C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, halogen, cyano, hydroxy, carboxy, C 1 -C 4 alkylamino or di (C 1 -C 4 alkyl) amino; R4gg is the stable nitroxyl radical, attached to the oxygen atom; R50o is unsubstituted or substituted C? -C? 8 alkyl, C2-C? 8 alkenyl, C3-C2o / -phenyl cycloalkyl, C7-Cn phenylalkyl; R501 is hydrogen, substituted or unsubstituted C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl C 3 -C 20 cycloalkyl, phenyl, 0 (C 1 -C 8 alkyl) ), 0 (C2-C18 alkenyl), phenylalkyl of C7-Cn, O-phenyl, 0-phenylalkyl of C7-C9 or halogen, CN, COOR500; CONR500R500; Q5 is CR502R503, CH = CH2, (CR502R503) n, CR504 = CR5o5- CR50 R507, (CR50 = CR505 ~ CR506R507)? Í C = CROS dO? R (C = CR508 509) nr 0, C = 0, NR510, NR5n-C = 0, 0-C (0) -0, S02, S, SiR5? 2R5i3, O-SIR512R513-O; R502, R503i R504, R505, Rs06r R5O7, R5O8, Rd09, R5IO, 5H R512 and R513 independently of each other are hydrogen, substituted or unsubstituted C? -C? 8 alkyl, C2-C? 8 alkenyl, C2 alkynyl -C? 8, C3-C7 cycloalkyl, phenyl, 0 (C? -C? 8 alkyl), 0 (C2-C? 8 alkenyl), C7-Cn phenylalkyl, 0-phenyl, 0-phenylalkyl C7-C9 or halogen; n is a number from 1 to 10; and it is a number from 1 to 25000 and; z is a number from 0 to 25000.
26. A polymer, characterized in that it is obtained according to step A) and B) of the process according to claim 1 or claim 2.
27. A polymer of «formula (P2), characterized claim
Qg is a homo, copolymer or tapered polymer resulting from the monomers given in claims 15 to 18; and t is a number from 0 to 25000. 28. A composition, characterized in that it comprises a) a polymeric radical initiator prepared according to step A) of claim 1 to claim 2 and b) an ethylenically unsaturated monomer or oligomer.
29. The use of a stable nitroxyl radical for the preparation of a grafted polymer according to claim 1 or claim 2.
30. The use of a grafted polymer according to step A) of claim 1 or claim 2 as macroinitiator for radical polymerization.
31. The use of the polymer obtained according to the process of claim 1 or claim 2 as an adhesive or as a compatibilizer for polymer blends or as agents for reinforcing polymers.