Title of Invention

A PROCESS FOR THE PREPARATION OF A GRAFTED POLYMER

Abstract

The present invention relates to a process for the preparation of a grafted polymer wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a nitroxyl-ether containing a group (=NO-X) up to a temperature between 150°C and 300°C and mixing it in the melt, wherein X is selected such, that cleavage of the o-x bond occurs and a radical X is formed at about the melting temperature of the polymer; and in a second step B) the grafted polymer of step A) is heated in the presence of an ethylenically unsaturated monomer or oligomer tp 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.

Full Text

Grafting of Ethylenicallv Unsaturated Monomers onto Polymers 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 compound containing a NO-ether to above the melting point of the polymer, mixing and reacting the components at said 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 to a temperature at which cleavage of the nitroxyl-polymer bond occurs. Further subjects of the present invention are grafted polymers prepared by said process, the intermediate polymeric radical initiator, the use of the polymeric radical initiator and the use of NO-ethers for grafting polymers. Increasing activities have been directed towards chemical modifications of existing polymers in order to obtain functional and/or engineered new materials. Chemical modifications of existing polymers are important for at least two reasons: 1. They can be an inexpensive and rapid way of obtaining new polymers without having to search for new monomers; 2. they may be the only way to synthesize polymers with the intended new characteristics. An important chemical modification is the free radical grafting of reactive monomers, which involves reaction of a polymer with a vinyl-group containing monomer or mixture of monomers capable of forming grafts onto the polymer backbone. If the grafts are long, the modified polymer becomes a true graft copolymer, of which the properties will be very different from those of the original polymer substrate. When the grafts are short with less than , for example five moieties, most of the physical and or mechanical properties of the modified polymer substrate will be retained. * The advantages of free radical-grafting are further gained with the use of batch mixers or screw extruders as chemical reactors, which allow the free radical-grafting reaction to occur without solvents. This is for example described by G. H. Hu et al., in "Reactive Modifiers for Polymers", first edition, Btackie Academic & Professional an Imprint of Chapman & Hall, London 1997, chapter 1, pages 1-97. These free radical-grafting reactions are usually performed in the presence of a free radical source such as a peroxide and a reactive monomer, such as for example acrylic acid. However the use of free radical sources such as peroxides may cause undesired properties and lead to problems during processing (gel formation, crosslinking, molecular weight reduction) or during use. Typically the long term stability is reduced and/or the polymer cannot anymore be used in outdoor applications or in applications at elevated temperatures. « US-A-4 581 429 to Solomon et al., issued April 8,1986, discloses 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 an initiator having the formula (in part) R'R"N-0-X, where X is a free radical species capable of polymerizing unsaturated monomers. Surprisingly it has now been found that with specific R'R"N-0-X compounds it is possible to produce a polymeric radical initiator by grafting the group R'R"N-0 to the polymer and to use this macroinitiator for further grafting reactions of olefinically unsaturated monomers, The polymerization processes and resin products of the present invention are useful in many applications, including a variety of specialty applications, such as for the preparation of grafted block copolymers which are useful as compatibiiizing agents for polymer blends or dispersing agents for coating systems. One subject of the present invention is a process for the preparation of a grafted polymer wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a nitroxyl-ether containing a group (=NO-X), wherein X is selected such, that cleavage of the 0-X bond occurs and a radical X is formed at about the melting temperature of the polymer; 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. The reaction mixture after step A) may also be cooled down to a temperature below 60° C before further reaction of step B) is performed. Optionally a free radical source is additionally present. The reaction mixture after step A) may also be cooled down to a temperature below 60° C before further reaction of step B) is performed. Preferably the free radical source is a bis-azo compound, a peroxide or a hydroperoxide. Specific preferred radical sources are 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl-butyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile). 2,2'-azobis(4-methoxy-2,4-dimethylvalero-nitriie), 1,1'-azobis(1-cyclohexanecarbonitnle), 2,2'-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2'-azobisisobutyrate, 2-(carbamoyla2o)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine), 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-hydroxyethyi]propionamide; acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate. t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyi peroxide, didecanoyi peroxide, dioctanoyi peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyi peroxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyi permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 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-butylperoxide, 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-dimethylhexyne-2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-a-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide. Peroxides are most preferred. Examples of suitable polymers are mentioned below. 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HOPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE). Poiyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or Vll! 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 that may be either p- or s-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegier (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE). 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, 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/aikyi 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 mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (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 (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of poiyalkylenes and starch. 5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene). 6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni-trile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo-lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso-prene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene. 7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maieimide 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 poiyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers. 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chlorideA/inyl acetate or vinylidene chloride/vinyl acetate copolymers. 9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate. 10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyi halide copolymers or acrylonitrile/alky! methacrylate/butadiene terpolymers. 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 phthalate or polyallyl melamine; as well as their copolymers with 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 which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes. acrylates or MBS. 14. Polyphenylene oxides and sulfides, 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 from 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 or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDf^ or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles. 18. Polyesters derived from dicarboxylic acids and diols and/or from 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 hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates. 20. Polysulfones, polyether sulfones and polyether ketones. 21. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA. PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic 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, styrene block-copolymers, polybutadiene orpolyisoprene, EPDM (ethylene-propylene diene monomer) or EPR (ethylene-propylene rubber). More preferred are polyethylene, polypropylene, polybutadiene, SBS and EPDM (ethylene-propylene diene monomer). One preferred nitroxyl-ether is of formula (X) V unsubstituted C1-C18alkyl, C2-C18alkenyl, C2-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3- C12cycloalkyl containing at least one nitrogen or oxygen atom; or C1-C18alkyl. C2-C18alkenyl, C2-C18 alkynyl, C7-C9phenylalkyl, Cs-Ciacycloalkyl or C3-C12Cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, which is unsubstituted or substituted by C1-C4alkyl. C1-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino; or R102 and R103, together with the linking carbon atom, form a C3-C12cycloalkyl radical, a (C4- C12cycloalkanon)-yl radical or a C3-C12cycloalkyl radical containing at least one O atom and/or a NR108 group; or if ni is 1 R104 is hydrogen, C1-C18alkyl, phenyl, an alkali metal cation or a tetraalkylammonium cation; R105 and R106 are hydrogen, C1-C18alkyl, C2-C18alkyl which is substituted by at least one hydroxy group or, taken together, form a C2-C12alkylene bridge or a C2-C12-alkylene bridge interrupted by at least one O or/and NRioa atom; R107 is hydrogen, C1-C18alkyl or phenyl; R108 is hydrogen, C1-18alkyl or C2-C18alkyl which is substituted by at least one hydroxy group; R109 is C1-C12alkylen or a direct bond; R110 is C4-C18alkyl bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylalkyl, C3- C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom; or C4-C18alkyl bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1- C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or'di(C1-C4alkyl)amino; if ni is 1 Rin is C1-Ciaalkyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom; or C1-C18alkyl, C7-C9phenylalkyt, C3-C12cycloalkyl or Ca-Ciscycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, d- C4aikylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino; or a polycyclic cycloaliphatic ring system or a polycyclic cycloaliphatic ring system with at least one di- or trivalent nitrogen atom; or R110 and Rm together form a C3-C12alkylene bridge, a C3-C12 alkylen-on bridge or a C2- C12alkylene bridge which is interrupted by at least one 0 or N atom, which bridges are unsubstituted or substituted with C1-C18alkyl, hydroxy(C1-C4)alkyl, phenyl, C7-C9phenylalkyj, NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino, R112 is hydrogen, -(Rio9)COORio4. cyano, -OR108. -SR108. -NHRios, -N(R108)2, -NH-C(0)-R108. unsubstituted C1-C18alkyl, C2-C18alkenyl, C2-C18alkynyl, C7-C9phenyialkyl, Ca-Cigcydoaikyl orCa- C12cycloalkyl containing at least one nitrogen or oxygen atom; or C1-Ciealkyl, C2-C18alkenyl, C2-C18 alkynyl, C7-C9phenyialkyl, C3-C12cycloalkyl or C3-C12cycloalkyl 'containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, Cr C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino, d((C1-C4alkyl)amino; or Rin and R^a together with the linking carbon atom form a C3-C12cycloalkyl radical. wherein Yi is O or CH2; Q is O or NR220, wherein R220 is hydrogen or C1-Ciealkyl; R201 is tertiary C4-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(0)-R222 wherein R221 is hydrogen, a alkali metal atom or C1-Ciealkyl and R222 is C1-Ciealkyl; or R201 is C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O 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 are independently C1-C18alkyl, benzyl, C5-C12cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222 or together with the carbon atom form a C2-C18cycloalkyl ring; if Y1 is O, R204 and R212 are OH, O(alkali-metal) C1-C18atkoxy, benzyloxy, NR223R224, wherein R223 and R224 are independently from each other hydrogen, CrCiaalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222; if Y1 is CH2. R204 is OH, C1-C18alkoxy, benzyloxy, 0-C(O)-{C1-C18)alkyl or NR223R224; R212 are a group C(O)R225. wherein R225 is OH, C1-C18alkoxy, benzyloxy, NR223R224, wherein R223 and R224 are independently from each other hydrogen, C1-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222; R205, R206» R207 and R208 are independently of each other C1-C18alkyl, C5-C12cycloalykyl or phenyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a C5-C12cycloalkyl ring; R209 and R210 are independently of each other hydrogen, formyl, C2-C18alkylcarbonyl, benzoyl, C1-C18alkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222; R211, is formyl, C2-C18alkylcarbonyl, benzoyl, C1-C18alkyl, C5-C12cycloalkyl, 05-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222. Still another preferred nitroxyl-ether contains a structural element of formula (XXX) Gn G2, G3, G4 are independently C1-Cealkyl or G1 and G2 or G3 and G4. or G1 and G2 and G3 and G4 together form a C5-C12cycioalkyl group; G5, G6 independently are H, C1-C18aikyl, phenyl, naphthyl or a group COOC1-C18alkyl. More preferred is a nitroxyl-ether, wherein the structural element of formula (XXX) is any of formulae A to S wherein Gi, G2, G3 and G4 are independently alkyl of 1 to 4 carbon atoms, or Gi and Gg together and G3 and G4 together, or G1 and G2 together or G3 and G4 together are pentamethylene; G5 and Ge are independently hydrogen or C1-C4 alkyl; R, if m is 1, is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ12 groups, in which Z12 is H, C1-C20alkyl, C3- C12alkenyl, C5-C7cycloaikyj, phenyl or benzyl; or R is a monovalent radical of a carbamic acid or phosphorus-containing acid or a monovalent silyl radical; R, if m is 2, is C2-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 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 having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ12 groups; or R is a divalent radical of a phosphorus-containing acid or a divalent silyl radical; R, if m is 3, is a tR1valent radical of an aliphatic, cycloaliphatic or aromatic tR1carboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZ12, of an aromatic tR1carbamic acid or of a phosphorus-containing acid, or is a tR1valent 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, R1 is C1-C12alkyl. C5-C7cycloalkyl, C7-C8aralkyl, C3-C12alkanoyI, C2-C8alkenoyI or benzoyl; when p is 1, R2 is C1-C18alkyl, C5-C7cycloalkyj, C2-C8aikenyl 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; or when p is 2, R2 is C2-C12alkylene, C6-C12-arylene, xylylene, a -CH2CH(OH)CH2-0-B-0-CH2CH(OH)CH2- group, wherein B is C2-C10alkylene, C6-C15arylene or C6-C12cycloalkylene; or, provided that R1 is not alkanoyl, alkenoyl or benzoyl, R2 can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO-; or R1 and R2 together when p is 1 can be the cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3- dicarboxylic acid; or R2is a group 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-tR1azinyl; when n is 1, R3 is C2-C8alkylene or hydroxyalkylene or C4-C22acyloxyalkylene; or when n is 2, R3 is (CH2)2C(CH2-)2; when n is 1, RA is hydrogen, CrC12alkyl, C2-C8alkenyl, C7-C9aralkyl, C5-C7cycloalkyl. C2-C4hydroxyaikyl, C2- Ce-alkoxyalkyl, Ce-C10-aryl, glycidyl, a group of formula -(CH2)m-COO-Q or of the formula - (CH2)m-0-C0-Q wherein m is 1 or 2 and Q is C1-C4-alkyl or phenyl; or when n is 2, R4 is C2-C12alkylene, Ce-Ciz-arylene, a group -CH2CH(OH)CH2-0-D-0-CH2CH(OH)CH2- wherein D is C2-C10alkylene, C6-C15arylene or C6-C12cycloalkylene, or a group - CH2CH(OZi)CH2-{OCH2CH(OZi)CH2)2- wherein Zi is hydrogen, CrCiaalkyl. ally!, benzyl, C2- C12alkanoyl or benzoyl; R5 is hydrogen. CrC12alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl; Qi is -N(R7)- or -0-; E is C1-C3alkylene, the group -CH2CH(R8)-0- wherein R8is hydrogen, methyl or phenyl, the group -(CH2)3-NH- or a direct bond; R7 is C1-C18alkyl, C5-C7-ycloalkyl, C7-C12aralkyl, cyanoethyl, Ce-C10aryl, the group -CH2CH(RQ)- OH; or a group of the formula wherein G is C2-C6alkylene or C6-C12arylene and R is as defined above; or Ryis a group -E-CO-NH-CH2-OR6; Re is hydrogen or C1-C18alkyl; Formula (F) denotes a recurR1ng structural unit of a oligomer where T is ethylene or 1,2- propylene, or is a repeating structural unit deR1ved from an a-olefin copolymer with an alkyl acrylate or methacrytate; k is 2 to.100; and R1o is hydrogen, C1-C12aikyi or C1-C12alkoxy; T2 has the same meaning as R4; T3 and T4 are independently aikylene of 2 to 12 carbon atoms, or T4 is a group where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; El and E2, being different, are each 0x0 or imino; E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, said phenyl or said naphthyl substituted by chloR1ne or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or said 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 said polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms; and E6 is an aliphatic or aromatic or aromatic tetravalent radical. Further suitable heterocyclic nitroxyl-ether are for example mentioned in WO 98/30601 or in 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-tR1decyl, n-tetradecyl, n-hexadecyl or n-octadecyl. The alkyl groups may be linear or branched. C3-C12alkyl which is interrupted by one or more oxygen atoms is preferably deR1ved from ethylene oxide or propylene oxide. C3-C12alkyl interrupted by at least one 0 atom is for example -CH2-CH2-0-CH2-CH3, -CH2-CH2-O-CH3 or -CH2-CH2-O-CH2-CH2-CH2-O-CH2-CH3. It is preferably deR1ved from polyethlene glycol. A general descR1ption is -((CH2)a-0)b-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10. C3-C12alkenyl is linear or branched and for example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyt, dodecenyl including their isomers. C3-C8alkynyl is preferably propargyl. C5-C12cydoalkyl is typically, cyC10pentyl, methyicyclopentyl, dimethylcyclopentyl, cydohexyl, methylcyclohexyl. Cycloalkyl which is interrupted by at least one O or N atom is for example 2-tetrahydropyran-yl, tetrahydrofurane-yl, 1,4 dioxan-yl, pyrrolidin-yl, tetrahydrothiophen-yl, pyrazolidin-yl, imidazolidin-yl, butyrolactone-yl, capro!actame-yl Examples for alkali metal are lithium, sodium or potassium. Alkyl substituted by-OH is typically 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl. C1-C18alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy. isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy, C1-C12alkyl substituted by C1-C8alkoxy, preferably by C1-C4alkoxy, in particular by methoxy or ethoxy, is typically 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxyropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl. C1-C12alkyl substituted by di(C1-C4alkyl)amino is preferably e.g. dimethylamino, diethylamino, 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl. C1-C18Alkyl substituted by C1-C4alkylamino is preferably e.g. methylamino, ethylamino, 2-methylaminoethyl, 2-ethylaminoethyi, 3-metfiylaminopropyl, 3-ethylaminopropyl, 3-butylamino-propyl and 4-ethylaminobutyl. C1-C4Alkylthio is typically tfiiomethyl, tfiioetfiyl, thiopropyl, thioisopropyl, thiobutyi and thioisobutyl, C2-C18 alkylcarbonyl is for example acetyl, propionyl, butyryl, pentylcarbonyl, hexylcarbonyl or dodecylcarbonyl. C7-C9phenylalkyl or C7-C9aralkyl is for example benzyl, phenylethyl, phenylpropyl, a.a-dimethylbenzyl or a-methylbenzyl. Examples of C2-C12alkylene bR1dges, preferably of C2-C6alkylene bR1dges, are ethylene, propylene, butylene, pentylene, hexylene. C2-C12aikylene bR1dges interrupted by at least one N or O atom are, for example, -CH2-O-CH2-CH2, -CH2'0-CH2"CH2'CH2, "CH2"0-CH2~CH2"CH2~CH2"i -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-CH2- or -CH2-NH-CH2-CH2-O-CH2-. Examples for C4-C12cycloalkanone-yl are cyclopentanone-yl, cyclohexanone-yl or cycloheptanone-yl. Phenyl substituted by 1, 2 or 3 C1-C4alkyl or C1-C4alkoxy is typically methyiphenyl, dimethyl-phenyl, tR1methylphenyl, t-butylphenyl, di-t-butylphenyl, 3,5-di-t-butyl34-methylphenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl. Examples of polycyclic cycloaliphatic R1ng systems are adamantane, cubane, twistane, norbornane, bycyclo[2.2.2]octane or bycyclo[3.2.1]octane. An example of a polycyclic heterocycloaliphatic R1ng system is hexamethylentetramine (urotropine). Examples of monocarboxylic acids with 1 to 18 carbon atoms are formic acid, acetic acid, propionic acid, phenyl acetic acid, cyclohexane carbonic acid, mono-, di- and tR1chlor-acetic acid or mono-, di- and tR1fluor-acetic acid. Other suitable acids are benzoic acid, chlor-benzoic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, chlorbenzenesulfonic acid, tR1fluormethanesulfonic acid, methylphosphonic acid or phenylphosphonic acid. Examples of a monovalent radical of a carboxylic acid are an acetyl, caproyi, stearoyi, acryloyi, methacryloyi, cyclohexylcarboxyiic acid, benzoyl or p-(3,5"di-tert-butyl"4-hydroxyphenyl)-propionyl radical. Further examples are deR1ved from propionic acid, lauR1nic acid or methyl ethyl acetic acid or the other isomers of valeR1c acid. Examples of a cycloaliphatic carboxylic acid is 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. Examples of a monovalent silyl radical are of the formula -{CiH2j)-Si(Z')2Z", in which j is an integer in the range from 2 to 5, and T and Z", independently of one another, are C1-C4alkyl or C1-C4alkoxy. Examples of di-, tR1- and tetra valent acids are for example malonyl, succinyl, glutaryl, adipoyi, suberoyi, sebacoyi, maleoyi, itaconyl, phthaloyi, dibutylmalonyl, dibenzylmalonyl, butyl(3,5"di-tert-butyl-4-hydroxybenzyl)malonyl or bicydoheptenedicarbonyl radical or a group of the formula Examples of a dicarbamic acid are the hexamethylenedicarbamoyi or 2,4-toluylenedicarbamoyl radicals. C2-C12alkanoyl is, for example, propionyl, butyryl. octanoyi, dodecanoyi, but preferably acetyl. Hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted alkyl can be, for example, 2-hydroxyethyl. 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl. Any C2-C12alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene. C4-C12alkenylene is for example butenylene, pentenylene, hexenylene, heptenylene or nonenylene including their isomers. C6-C12arylene is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene. C4-C22acyioxya!kylene is^ for example, 2-ethyl-2-aoetoxymethylpropylene. Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyt, isopropoxyethyl or propoxypropyl. C1-C18alkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy. The nitroxyl-ethers of formula (X) are known and may be prepared according to WO 99/03984, EP-A-0 891 986 or WO 98/13392. Some typical examples are given below. The nitroxyl-ethers of formula XXa, b and c are also known and may be prepared according to European Patent Application No. 98810741.3. Typical examples are given below. The nitroxyl-ethers of formula XXX are also known and can be prepared as descR1bed in European Patent Application No. 98810531.8. Furthermore DE 26 21 841, US 4*131 *599 and DE 26 30 798 for example descR1be the preparation of 2,6-diethyl-2,3,6-tR1methyl-4-oxopipeR1dine and 2,6-dipropyl-3-ethyl-2,6-dimethyl- 4-oxo-pipeR1dine, which are intermediates for the corresponding 1-oxo and nytroxyl-ether compounds. Another method for the preparation of 2,2-dimethyl-6,6-dialkyl-4-oxopipeR1dine is descR1bed 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). The oxidation of the pipeR1dine compound to 1-oxo-pipeR1dine deR1vatives is well known in the art and for example descR1bed by L.B. Volodarsky, V. A. Reznikov, V.I. Ovcharenko in Synthetic Chemistry of Stable Nitroxides, CRC Press, Boca Raton 1994. The tetramethylpipeR1dine precursors are partially commercially available or can be prepared according to known methods. For example US 5 096 950 and the documents cited therein descR1be the preparation of the precursors. The oxidation and ether forming process can be done as descR1bed above. Examples are given below. Preferably Gi, G2, G3 and G4 are methyl or ethyl and G5 and Ge are hydrogen or methyl. More Preferably G1, G2, G3 and G4 are methyl and G5 and Ge are hydrogen. Another preferred group of compounds are those wherein G1 and G3 are ethyl and G2 and G4 are methyl, or G1 and G4 are ethyl and G2 and G3 are methyl, and one of G5 or G6 is hydrogen and the other methyl or both are hydrogen. Preferably X is selected from the group consisting of C1-C18alkyl, C5-C12alkenyl, Ca-Ciealkinyl, phenyl, phenyl(C7-Cii)alkyl, phenyl or phenyl(C7-Cii)alkyl substituted by CrC12atkyl, C1-C12alkoxy, OH, amino, CrC12alkylamino, C1-C12dialkylamJno, NO2 or halogen, C2-C7cycloalkyl, or a group R20, R21. and R22 are hydrogen or C1-C12alkyl, C2-C12alkenyl, phenyl or C5-C7cycloalkyl. More preferably X is selected from the group consisting of C1-C18alkyl, benzyl, ailyl, cyclopentyl or cyclohexyl. Most preferred are allyl and cyclohexyl. A preferred subgroup are compounds of the structural formulae A, B, O or P, wherein m is 1, R is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, giycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 1£ 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 havinc 7 to 15 carbon atoms; pis 1; R1 is CrC12alkyl, C5-C7cycloalkyl, Cy-Cearalkyl, C2-C18alkanoyi, Cs-CsalkenoyI or benzoyl; R2 is C1-C18alkyl, C5-C7cycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is giycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl. More preferred are those of structure A or B, wherein R is hydrogen, C1-C18alkyl, cyanoethyl, benzoyl, giycidyl, a monovalent radical of an aliphatic carboxylic acid, having 2 to 18 carbon atoms; R1 is CrC12alkyl, C7-C9aralkyl, C2-C18alkanoyl, Cs-CsalkenoyI or benzoyl; R2 is C1-C18alkyl, glycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl. Another preferred subgroup is wherein the nitroxyl-ether is a compound of formula (X), ni is 1 R1oi is cyano; R102 and R103 are each independently of one another unsubstituted C1 -C12alkyl or phenyl; or R102 and R103, together with the linking carbon atom, form a C5-C7cycloalkyl radical; R110 is C4-C12alkyl bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylalkyl or phenyl; or Rno and Rm together form a C2-C6alkylene bR1dge which is unsubstituted or substituted with C1-C4alkyl; and R1i2isC1-C4alkyl. A further preferred subgroup is wherein the nitroxyl-ether is a compound of formula (XXa), YisO; R201 is tertiary C2-C8alkyl; R202 and R203 are methyl, ethyl or together with the carbon atom form a C5-C6cyC10alkyl R1ng; R204 is C1-C18alkoxy, benzyloxy or NR223R224, wherein R223 and R224 are independently of each other hydrogen or C1-Caalkyl; or of formula (XXb), wherein Qi is O; R205. R206, R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a Cg-CecyC10alkyl R1ng; R209 and R210 are independently of each other formyl, C2-C8alkylcarbonyl, benzoyl, d-Cealkyl, benzyl or phenyl; or of formula (XXc), wherein Yi is O; R205. R206, R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a C5-C6cycloalkyl R1ng; R211 is formyl, C2-C18alkylcarbonyl, benzoyl, C1-Cieaikyi, benzyl or phenyl and » R212 is OH, C1-C18alkoxy, benzyloxy, NR223R224, wherein R223 and R224 are independently of each other hydrogen or C1-C18alkyl. Preferably the polymer to be grafted on contains unsaturated moieties selected from the group consisting of polydienes, co-, block-, random- and tapered polymers of styrene, terpolymers with diolefins and copolymers with diolefins. Preferred unsaturated polymers are poiybutadiene, polyisoprene, styrene-isoprene-block-copolymers (SI, SIS), styrene-butadiene-block-copolymers (SB, SBS, SEBS), ABS, EPDM. butyl rubber, chloroprene rubber and nitR1le rubber having a content of unsaturated repeating units from 0.1 to 85%. Mostly preferred are SB, SBS. EPDM having a content of unsaturated repeating units from 1 to 70%. Preferably the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes. acrolein, vinyl acetate, (alkyl)acrylic acidanhydR1des, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides. More preferably the ethylenically unsaturated monomer is styrene, a-methyi styrene, p-methyl styrene or a compound of formula CH2=C(Ra)-(C=Z)-Rb, wherein Ra is hydrogen or C1-C4alkyl, Rb is NH2, OCH3, glycidyl, unsubstituted C1-C18alkoxy or hydroxy-substituted C1-C18alkoxy, unsubstituted C1-C18alkylamino, di(C1-C18alkyl)amino, hydroxy-substituted C1-C12alkylamino or hydroxy-substituted di(C1-C18alkyl)amino; Me is a monovalent metal atom Z is oxygen or sulfur. Most preferably Ra is hydrogen or methyl, Rb is NH2, gycidyl, unsubstituted or with hydroxy substituted C1-C4alkoxy, unsubstituted C1-C4alkylamino, di(C1-C4alkyl)amino, hydroxy-substituted C1-C4alkylamino or hydroxy-substituted di(C1-C4alkyl)amino;and Z is oxygen. Specifically preferred ethylenically unsaturated monomers are methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butyiacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates, acrylonitR1le, acryiamide or methacrylamide. The temperature applied in the first reaction step depends on the polymer and is for example 50° to 150° C above the glass transition temperature (Tg) for amorphous polymers and 20° to 180° C above the melting temperature (Tm) for semi-crystalline polymers. Typical are following temperatures: low density polyethylene LDPE 170-260° C high density polyethylene HOPE 180-270° C polypropylene PP 180-280° C polystyrene PS 190-280° C styrene-block copolymers SB(S) 180-260° C ethylene-propylene-diene modified EPDM 180-260° C ethylene propylene rubber EPR 180-260° C In a preferred process the temperature in the first step A) is from 150° C to 300° C, more preferred from 170° C to 280° C. Preferably the temperature in the second step B) is from 70° to 280° C, more preferably from 70° to 210° C. If a temperature of 120° to 180° C is applied, the group X is preferably allyl or benzyl. If a temperature of 180° to 240° C is applied the group X is preferably benzyl or cyclohexyl. If a temperature of 240° to 300° C is applied the group X is preferably cyclohexyl or alkyl. Preferably the compound containing a structural element of formula (I) is present in an amount from 0.1% to 30%, more preferably in an amount from 1% to 20% and most preferably in an amount from 1% to 10% based on the weight of the polymer. Preferably the ratio of the reaction product of step A) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1:10000 to 10:1, more preferably from 1:1000 to 1:1 and most preferably from 1:500 to 1:1. Step A) of the process may be performed in any reactor suitable for mixing a polymer melt. Preferably the reactor is an extruder or kneading apparatus as for example descR1bed in "Handbuch der Kunststoffextrusion" Vol.1, editor F. Hensen, W. Knappe and H. Potente, 1989, pages 3-7. If an extruder is used the process may be descR1bed as reactive extrusion process. Examples of reactiv extrusion equipment and processes are given by G. H. Hu et al., in "Reactive Modifiers for Polymers", first edition, Blackie Academic & Professional an ImpR1nt of Chapman & Hall, London 1997, chapter 1, pages 1-97. Preferably, if an extruder is used, a reduced pressure of less than 200 mbar is applied duR1ng extrusion. Volatile byproducts are removed thereby. The reaction time for step A) depends on the desired amount of grafted ONR'R" initiator moieties. Typical reaction times are from a few minutes to an hour. Preferably the reaction time is from 1 min to 1 h, most preferably from 2 min to 20 min. The reaction step B) may be performed immediately after step A), however it is also possible to store the intermediate polymeR1c radical initiator at room temperature for some time. The intermediate polymeR1c radical initiator is stable at room temperature and no loss of activity occurs up to several months. The reaction for step B) may be performed in any reactor suitable for mixing a polymer melt with a monomer. The degree of grafting depends on the reaction time, on the temperature used and the activity of the polymeR1c initiator. Preferably the reaction time for step B) is from 1 min to 20 hours, more preferably from 30 min to 5 hours. If the reaction step B) is performed in 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 modification agents, nucleating agents, coupling agents between filler and polymer matR1x or dispersing agents. The process is particularly useful for the preparation of grafted block copolymers. Grafted block copolymers are, for example, grafted block copolymers of polystyrene and polyacrylate (e.g., poly(styrene-co-acrylate) or poly(styrene-co-acrylate-co-styrene). They are usefull as adhesives or as compatibilizers for polymer blends or as polymer toughening agents. Poly(methylmethacrylate-co- acrylate) diblock graft copolymers or poly(methylacrylate-co-acrylate-co-methacrylate) tR1block graft copolymers are useful as dispersing agents for coating systeme, as coating additives (e.g. rheological agents, compatibilizers, reactive diluents) or as resin component in coatings(e,g. high solid paints) Graft'block copolymers of styrene, (meth)acrylates and/or acrylonitR1le are useful for plastics, elastomers and adhesives. Furthermore, graft block copolymers of this invention, wherein the grafted blocks have polar monomers on a non polar polymer are useful in many applications as amphiphilic surfactants or dispersants for prepaR1ng highly uniform polymer blends. Thus, the present invention also encompasses in the synthesis novel graft block, multi-block, star, gradient, random, hyperbranched and dendR1tic copolymers. The polymers prepared by the present invention are particularly useful for following applications: adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubR1cants, rheology modifiers, thickeners, crossiinkers, paper treatment, water treatment, electronic mateR1als, paints, coatings, photography, ink mateR1als, imaging mateR1als, superabsorbants, cosmetics, hair products, preservatives, biocide mateR1als or modifiers for asphalt, leather, textiles, ceramics and wood. Because the present graft polymeR1zaton is a "living" polymeR1zation, it can be started and stopped practically at will. Furthermore, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymeR1zation in a living matter. Thus, in one embodiment of this invention, once the first monomer is consumed in the initial polymeR1zing step a second monomer can then be added to form a second block on the growing graft polymer chain in a second polymeR1zation step. Therefore it is possible to carry out additional graft polymeR1zations with the same or different monomer(s) to prepare multi-block graft copolymers. Furthermore, since this is a radical polymeR1zation, graft blocks can be prepared in essentially any order. Consequently further subjects of the present invention are a polymeR1c radical initiator prepared according to step A) of the process without an additional free radical source and a polymeR1c radical initiator prepared according to step A) of the process with an additional free radical source. Another subject of the invention are the grafted polymers obtainable by according to A) and B) of the process descibed above. The polymeR1c radical initiator obtainable by step A) of the above process is schematically represented in formula (P1) • R498 is hydrogen, substituted or unsubstituted C1-C18alkyl, C2-C18alkenyl, C2-C18alkinyl; C3-C2ocycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy; C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino, 0(C1-C18alkyl), 0(C2-C18alkeny), Cy-Cnphenylaikyl, 0-phenyl, OC7-C9phenylalkyl or halogen or phenyl and naphthyl which are unsubstituted or substituted by C1-C4alkyl, Cr C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4a!kyiamino or di(C1- C4alkyt)amino; R499 is the stable nitroxyl radical, bound at the oxygen atom; R500 is substituted or unsubstituted C1-C18alkyl, Cg-Cisalkenyl, C3-C20cycloalkyl, phenyl, C7- Cnphenylalkyl; R501 is hydrogen, substituted or unsubstituted C1-C18alkyl, C2-C18alkenyl, C2-C18alkinyl, C3- Caocycloalkyl, phenyl, 0(C1-C18alkyl), 0(C2-C18alkeny), C7-Ciiphenyialky(. 0-phenyl, O- Cr Cgphenylalkyl or halogen, CN, COOR500, CONR500R500; Q5 is CR502R5031 CH=CH2, (CR502R503)ni CR504=CR505-CR506R507. (CR5O4=CR5O5-CR506R507)ni C=CR508R509. (C=CR508R509)n, O, C=0, NR510, NRsirC^O, 0-C(O)-0, SO2, S, SiRgiaRsia. O- SiRsiaRsia^O; R5021 R503, R504. R5051 R506. R5071 R508. R509, R510. R5111 Rsi2 and R513 independently of each other are hydrogen, substituted or unsubstituted C1-Ciealkyl, C3-C12alkenyl, C2-C18alkinyi, C3- C/cyC10alkyl, phenyl, 0(C1-C18alkyl), ©(C2-C18alkeny), Cy-Cnphenyialkyl, 0-phenyl, O- C7- Cgphenyialkyl or halogen; n is a number from 1 to 10; y is a number from 1 to 25000 and; z is a number from 0 to 25000. Preferably R501 is H or methyl; Q5 is CR502R503, CH=CH2, CR504=CR505CR506R507. wherein R502 and R503 is H, methyl or C2-Cgalkenyl and R504, R505. R506 and R507 are independently H or methyl. Examples for the different substituents have been already given. Within this selection polyethylene, polypropylene and polybutadiene, SBS and EPDM are especially preferred. A further subject of the invention is a polymer of formula (P2) obtainable by step B) of the above process. Definitions and examples of the substituents are as given above; Q6 is a homo-, co- or tapered polymer resulting from the monomers as descR1bed above, t is a number from 0 to 25000. R499 may be removed thermally or chemically. Preferably the polymer (P2) is grafted with a monomer selected from the groups descR1bed above and more preferably with styrenes, (meth)acrylates. butadiene, isoprene. Most preferred are SB-g-styrenes, SB-gf-(meth)acrylates, Sl-g-styrenes, Sl-5f-(meth)acrylates, SBS-gF-styrenes, SBS-p-(meth)acrylates, EPDM-g-styrenes, EPDM-g-(meth)acrylates. Examples and preferences have been already given, A further subject of the present invention is the use of a nitroxyl-ether containing a group (=N0-X), wherein X is selected such, that cleavage of the 0-X bond occurs and a radical X« is formed at about the melting temperature of the polymer for the preparation of a grafted polymer with and without a free radical source. Still further subjects are the use of a grafted polymer according to step A) of the above descR1bed process as macroinitiator for radical polymeR1zation, and the use of the polymer obtained according to the process as adhesive or as compatibilizer for polymer blends or as polymer toughening agent. The following examples illustrate the invention. A) Grafting of N-OR compounds to the polvmer (preparation of a polvmeR1c initiator) * Polypropylene (MFR230/2.I6 = 1.43 according to ISO 1133) is extruded together with the compounds given in Table 2 in a twin screw extruder (TW 100 of Haake, Germany) at 180 -210° C (heating zones 1-5) and 40 rpm. The melt viscosity (MFR) is determined according to ISO 1133 (Table 1). The granulated polymer is dissolved, reprecipitated and high temperature NMR spectra are taken to determine whether polymer bound NO-moieties are present. B) Grafting of N-OR to the polymer and subsequent polymer analogous reaction Commercially available SBS (styrene/butadiene/styrene copolymer, Kraton D 1102 CU, supplier: Shell) is extruded together with the compound given in Table 2 in a twin screw extruder (TW 100 of Haake, Germany) at 180 - 210° C (heating zones 1-5) and 40 rpm. In an evacuated Schlenk reactor, purged with argon, 5 g of the granulated polymer is dissolved in 50-100 mL monomer under argon atmosphere. Dissolved oxygen is removed in freeze-thaw-cycles (liquid nitrogen). The reaction mixture is stirred and heated under argon atmosphere. Remaining monomer is removed under vacuum and the residue is dR1ed under vacuum until constant weight is achieved. Molecular weights and molecular weight distR1butions are determined by gel permeation chromatograpgy (GPC). The results are shown in Table 3. Claims 1. A process for the preparation of a grafted polymer wherein in a first step A) a stable nitroxyl radical is grafted onto a polymer, which step comprises heating a polymer and a nitroxyl-ether containing a group (=NO-X), wherein X is selected such, that cleavage of the 0-X bond occurs and a radical X is formed at about the melting temperature of the polymer; 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. 2. A process according to claim 1, wherein a free radical source is additionally present. 3. A process according to claim 2, wherein the free radical source is a bis-azo compound, a peroxide or a hydroperoxide. 4. A process according to claim 3 wherein the free radical source is 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl-butyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1-azobis(1 -cyclohexanecarbonitrile), 2,2'-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2'-a2obisisobutyrate, 2-(carbamoylazo)tsobutyronitn!e, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine), 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-hydroxyethyljpropionamide; acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyi peroxide, didecanoyi peroxide, dioctanoyi peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyi peroxide, t-butyl per 2-ethy!hexanoate, bis-(4-chlorobenzoyl)-peroxide, 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 perisononaoate, 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-butylperoxide, 3-t-butylperoxy 3-phenytphthalide,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-dimethylhexyne-2,5-cli-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cydononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropyibenzene mono-a-hydroperoxide, cumene hydroperoxide or t-butyi hydroperoxide. 5. A process according to claim 1 wherein the polymer is polyethylene, polypropylene, polystyrene, styrene block-copolymers, polybutadiene or polyisoprene, EPDM (ethylene- propylene diene monomer) or EPR (ethylene-propylene rubber). 6. A process according to claim 1, wherein the nitroxyl-ether is of formula (X) wherein ni is 0 or 1 R10i, R102, R103 are each independently of one another hydrogen, halogen, NO2, cyano, -CONR105R106, -(R109)COOR104. -C(0)-R107, -OR108, -SR10s. -NHR10e, N(R108)2, carbamoyl, di(Ci- Ci8alkyl)carbamoyl,-C(=NR105)(NHR106); unsubstituted C1-C18alkyI, C2-C18alkenyi, C2-C18alkynyl, Cr-CgphenyJalkyl, C3-C12cycloalkyI or C3- Ciacycloalkyl containing at least one nitrogen or oxygen atom; or C1-C18alkyl, C2-C18alkenyl, C2-C18 alkynyl, Cy-Cgphenyialkyl, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, CrC4alkylamino ordi(CrC4alkyl)amino; or phenyl, which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(CrC4alkyl)amino; or R102 and R103. together with the linking carbon atom, form a C3-C12cycioalkyl radical, a (C4- C12cycloalkanon)-yl radical or a C3-C12cycloalkyI radical containing at least one O atom and/or a NR108 group; or if ni is 1 R104 is hydrogen, C1-C18alkyI, phenyl, an alkali metal cation or a tetraalkylammonium cation; R105 and R10e are hydrogen, C1-C18alkyl. C2-C18alkyl which is substituted by at least one hydroxy group or, taken together, form a C2-C12alkylene bridge ora C2-C12-alkylene bridge interrupted by at least one O or/and NR10s atom; R107 is hydrogen, C1-C18alkyI or phenyl; R108 is hydrogen, C1-C18alkyI or C2-C18alkyl which is substituted by at least one hydroxy group; R109 is C1-C12alkylen or a direct bond; R110 is C4-Ci8alkyl bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylalkyl, C3- C12cycloalkyl or C3-C12cycloaikyi containing at least one nitrogen or oxygen atom; or C1-C18alkyI bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylalkyl, C2-C18cycloalkyI or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, Cr C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino; if Hi is 1 R111 is C1-C18alkyI, C7-C9phenylalkyI, C3-C12cycloalkyl or C3-C12cycloalkyI containing at least one nitrogen or oxygen atom; or C1-C18alkyI, C7-C9phenylalkyI, C3-C12cycloalkyI or C3-C12cycioalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino ordi(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, Cr C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino; or a polycyclic cycloaliphatic ring system or a polycyclic cycloaliphatic ring system with at least one di- or trivalent nitrogen atom; or R110 and R111 together form a C2-C12alkylene bridge, a C3-C12alkylen-on bridge or a C2- C12alkylene bridge which is interrupted by at least one O or N atom, which bridges are unsubstituted or substituted with C1-C18alkyI, hydroxy(C1-C4)alkyl, phenyl, Cr-CgphenylalkyI, NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino, R112 is hydrogen, -{R109)COOR104. cyano, -OR10a. -SR10a, -NHR10a. -N(R108)2. "NH-C(0)-R108. unsubstituted C1-C18alkyI, C2-C18alkenyl, C2-C18alkynyl, C7-C9phenylaikyj, G3-C12cycloalkyl orCs- C12cycloalkyl containing at least one nitrogen or oxygen atom; or C1-C18alkyI, C2-C18alkenyl, C2-C18 alkynyl, C7-C9phenylalkyI, C3-C12cycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy. d-C4alkyIthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino, di(C1-C4a!kyl)amino; or R111 and R112 together with the linking carbon atom form a C3-C12cycloaikyl radical. wherein Y1 is O or CH2; Q is O or NR2201 wherein R220 is hydrogen or C1-C18alkyI; R201 is tertiary C4-Ci8alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222 wherein R221 is hydrogen, a alkali metal atom or C1-C18alkyI and R222 is C1-C18alkyI; or R201 is C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, a polycyclic alky! radical or a polycyclic alky! radical which is interrupted by at least one O or N atom; R202 and R203 are independently C1-C18alkyI, benzyl, Cs-C12cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222 or together with the carbon atom form a C5-C12cycloalkyl ring; ifY1 isO, R204 and R212 are OH, O(alkali-metal) C1-C18alkoxy, benzyloxy, NR223R224. wherein R223 and R224 are independently from each other hydrogen, C1-C18alkyI or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222; if Yi is CH2. R204 is OH, C1-C18alkoxy, benzyloxy, 0-C(O)-(C1-Ci8)alkyl or NR223R224; R212 are a group C(O)R225. wherein R225 is OH, C1-C18alkoxy, benzyloxy, NR223R224. wherein R223 and R224 are independently from each other hydrogen, C1-C18alkyI or phenyl, which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222; R205. R206. R207 and R208 are independently of each other C1-C18alkyI, C5-C12cycloalykyl or phenyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a C3-C12cycloalkyI ring; R209 and R210 are independently of each other hydrogen, formyl, C2-C18alkylcarbonyl, benzoyl, C1-C18alkyI, C5-C12cycloalkyl, C3-C12cycloaikyI which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted" by halogen, OH, COOR221 or C(O)-R222; R211. is formyl, C2-C18alkylcarbonyl. benzoyl. CrCiealkyl. C2-C12cycloalkyi, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR221 or C(O)-R222. 8. A process according to claim 1, wherein the nitroxyl-ether contains a structural element of formula (XXX) G1. G2, G3. G4 are independently C1-C6alkyI or G1 and G2 or G3 and G4. or G1 and G2 and G3 and G4 together form a Cs-C12cycloalkyI group; G5. Ge independently are H, C1-C18alkyI, phenyl, naphthyl or a group COOC1-C18alkyl. 9. A process according to claim 8, wherein the the structural element of formula (XXX) is any of formulae A to S wherein G1, G2, G3 and G4 are independently aikyi of 1 to 4 carbon atoms, or G1 and G2 together and G3 and G4 together, or G1 and G2 together or G3 and G4 together are pentamethylene; G5 and Ge are independently hydrogen or C1-C4 alkyl; R, if m is 1, is hydrogen, C1-C18alkyI which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ12 groups, in which Z12is H, C1-C20alkyl, C3- C12alkenyl, Cs-CycycloaJkyl, phenyl or benzyl; or R is a monovalent radical of a carbamic acid or phosphorus-containing acid or a monovalent silyl radical; R. if m is 2, is C2-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 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 having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ12 groups; or R is a divalent radical of a phosphorus-containing acid 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 moiety by -COOZ12, of an aromatic tricarbamic acid or of 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. Ri is C1-C12alkyl. Cs-Cycycloalkyi, C7-C8aralkyl, C3-C12aikanoyl, Ca-CsalkenoyI or benzoyl; when p is 1, R2 is C1-C18alkyi, Cs-Cycycloalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z- or -CONH-Z wherein Z is hydrogen, methyl or phenyl; or when p is 2, R2 is C2-C12alkyiene, C6-C12-arylene, xylylene, a -CH2CH(OH)CH2-0-B-0-CH2CH(OH)CH2- group, wherein B is C2-C10alkylene, Ce-Cisarylene or C6-C12cycloalkylene; or, provided that Ri is not alkanoyl, alkenoyl or benzoyl, R2 can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO-; or Ri and R2 together when p is 1 can be the cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3- dicarboxylic acid; or R2is a group where T? and Ta are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T7 and Te 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-C8alkylene or hydroxyalkylene or C4-C22acyioxyalkylene; or when n is 2, R3 is (-CH2)2C(CH2-)2; when n is 1. R4 is hydrogen, C1-C12alkyi. Ca-Csalkenyl, C7-C9aralkyl, Cs-CycycloalkyI, C2-C4hydroxyalkyl, C2- Ce-alkoxyalkyI, C6-C10-aryl, giycidyl, a group of formula -(CH2)m-C00-Q or of the formula - (CH2)m-0-C0-Q wherein m is 1 or 2 and Q is C1-C4-alkyl or phenyl; or when n is 2, R4 is C2-C12alkylene, C6-C12-arylene, a group -CH2CH(OH)CH2-0-D-0-CH2CH(OH)CH2- wherein D is C2-Cioalkylene, C6-C15aryJene or C6-C12cycloalkylene, or a group - CH2CH(OZi)CH2-(OCH2CH(OZi)CH2)2-wherein Z, is hydrogen, C1-C18aikyl, allyl, benzyl, C2- C12a!kanoyl or benzoyl; R5 is hydrogen, C1-C12alkyi, allyl. benzyl, glycidyl or C2-C6alkoxyalkyl; Qi is -N(R7)- or -0-; E is CrCaalkylene, the group -CH2CH(R8)-0- wherein Rsis hydrogen, methyl or phenyl, the group -(CH2)3-NH- or a direct bond; R7 is C1-C18alkyi, Cs-Cy-ycloalkyl, C7-C12aralkyl, cyanoethyl, C6-C10aryl, the group -CH2CH(Ra)- OH; or a group of the formula wherein G is C2-C6alkylene or C6-C12aryiene and R is as defined above; or Rris a group -E-CO-NH-CH2-OR6; Re is hydrogen or C1-C18alkyI; Formula (F) denotes a recurring structural unit of a oligomer where T is ethylene or 1,2- propylene, or is a repeating structural unit derived from an a-olefin copolymer with an alkyl acrylate or methacrylate; k is 2 to 100; and R^o is hydrogen, C1-C12alkyl or C1-C12alkoxy; T2 has the same meaning as R4; T3 and T4 are independently alkylene of 2 to 12 carbon atoms, or T4 is a group where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; ■ El and E2. being different, are each 0x0 or imino; E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyi, said phenyl or said naphthyl substituted by chlorine or by alky! of 1 to 4 carbon atoms, or phenylalkyi of 7 to 12 carbon atoms, or said phenylalkyi substituted by alkyl of 1 to 4 carbon atoms; E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyi of 7 to 12 carbon atoms; or E3 and E4 together are polymethylene of 4 to 17 carbon atoms, or said polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms; and Ee is an aliphatic or aromatic or aromatic tetravalent radical. 10. A process according to claim 8, wherein G1, G2, G3 and G4 are methyl and G5 and Ge are hydrogen. 11 .A process according to claim 1, wherein X is selected from the group consisting of C r Ciealkyl, C3-C18aikenyl, C3-C18alkinyl, phenyl, phenyl(C7-C11)alkyl, phenyl or phenyl(C7-Cii)alkyl substituted by C1-C18alkyI, C1-C12alkoxy, OH. amino, C1-C12alkylamino, C1-C18dialkylamino, NO2 12. A process according to claim 11, wherein X is selected from the group consisting of C1-C18alkyl, benzyl, allyl, cyclopentyi or cyclohexyl. 13. A process according to claim 9, wherein the nitroxyl-ether is of the structural formulae A, B, O or P, wherein m is 1, R is hydrogen, C1-C18alkyI which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p- unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; pisi; Ri is C1-C12alkyl, C5-C7cycloalkyI, Cy-C5aralkyI, C2-C18alkanoyl, C3-CalkenoyI or benzoyl; R2 is C1-C18alkyl, C5-C7cycloalkyi, C2-C8alkenyi unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl. 14. A process according to claim 13, wherein the nitroxyl-ether is of the structural formula A or B, wherein R is hydrogen, C1-C18alkyI, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid, having 2 to 18 carbon atoms; Ri is C1-C12alkyl, Cy-CsaralkyI, C2-C18alkanoyl, C3-C5alkenoyI or benzoyl; R2 is C1-C18alkyI, glycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl. 15. A process according to claim 6, wherein the nitroxyl-ether is a compound of formula (X), ni is 1 R101 is cyano; R102 and R103 are each independently of one another unsubstituted Ci -CisalkyI or phenyl; or R102 and R103, together with the linking carbon atom, form a C5-C7cycloalkyl radical; R110 is C4-C12alkyl bound via a tertiary C-atom to the nitrogen atom, C9-C11phenylaikyj or phenyl; or Rno and R111 together form a C2-C6alkylene bridge which is unsubstituted or substituted with C1-C4alkyl; and Rn2isC1-C4alkyl. 16. A process according to claim 6, wherein the nitroxyl-ether is a compound of formula (XXa), YisO; R201 is tertiary C4-C8alkyl; R202 and R203 are methyl, ethyl or together with the carbon atom form a C2-C6cycloalkyI ring; R204 is C1-C18alkoxy, benzyloxy or NR223R2241 wherein R223 and R224 are independently of each other hydrogen or C1-C8alkyI; or of formula (XXb), wherein Qi is O; R205, R206. R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a C2-C6cycloalkyI ring; R209 and R210 are independently of each other formyl, C2-C8alkylcarbonyl, benzoyl, CrCaalkyI, benzyl or phenyl; or of formula (XXc), wherein Yi is 0; R205, R2061 R207 and R208 are independently of each other methyl or ethyl; or R205 and R206 and/or R207 and R208 together with the carbon atom form a C2-C6cycloalkyi ring; R211 is formyl, C2"Ci8alkylcarbonyl, benzoyl, d-Ctaalkyl, benzyl or phenyl and R212 is OH, C1-C18alkoxy, benzyloxy, NR223R224. wherein R223 and R224 are independently of each other hydrogen or C1-C18alkyl. 17. A process according to claim 1, wherein the polymer to be grafted on contains unsaturated moieties selected from the group consisting of polydienes, co-, block-, random- and tapered polymers of styrene, terpolymers with diolefins and copolymers with diolefins. » 18. A process according to claim 1, wherein the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides. 19. A process according to claim 18, whrein the ethylenically unsaturated monomer is styrene, a-methyl styrene. p-methyl styrene or a compound of formula CH2=C(Ra)-(C=Z)-Rb, wherein Ra is hydrogen or C1-C4alkyl, Rb is NH2, OCH3, glycidyl, unsubstituted C1-C18alkoxy or hydroxy-substituted C1-C18alkoxy, unsubstituted C1-C18alkylamino, di(C1-Ci8alkyl)amino, hydroxy-substituted d-Ciealkylamino or hydroxy-substituted di(C1-C18alkyl)amino; Me is a monovalent metal atom Z is oxygen or sulfur. 20. A process according to claim 1. wherein the temperature in the first step A) is from 150° C to 300° C. 21. A process according to claim 1, wherein the temperature in the second step B) is from 70° to 280° C. 22. A process according to claim 1, wherein the compound containing a structural element of formula (I) is present in an amount of from 0.1% to 30% based on the weight of the polymer. 23. A process according to claim 1, wherein the ratio of the reaction product of step A) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1:10000 to 10:1. 24. A process according to claim 1, wherein the first step A) is performed in an extruder. 25. A polymeric radical initiator obtainable according to step A) of claim 1 or claim 2. 26. A polymer obtainable according to steps A) and B) of the process of claim 1 or claim 2. 27. A polymeric radical initiator of formula (PI) R498 is hydrogen, substituted or unsubstituted C1-C18alkyI, C3-C12alkenyl, C2-C18alkinyl; C3-C2ocycloalkyl or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom or C3-C12cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy; C1-C4alkoxy, C1-C4alkylthio, CrCAaikyiamino or di(C1-C4alkyl)amino, ©(C1-C18aJkyl), 0(C2-C18alkeny). Cy-CiiphenyiaJkyJ, 0-phenyl, OC7-C9phenylalkyi or halogen or phenyl and naphthyl which are unsubstituted or substituted by C1-C4alkyl, Cr C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(Cr C4alkyl)amino; R499 is the stable nitroxyl radical, bound at the oxygen atom; R500 is substituted or unsubstituted C1-C18alkyI, C2-C18alkenyl, C3-C2ocycloalkyl, phenyl, C7- Ciiphenylalkyl; R501 is hydrogen, substituted or unsubstituted C1-C18alkyI, C3-C12alkenyj, C2-C18alkinyl, C3- C2ocycloalkyl. phenyl, 0(C1-C18alkyl), 0(C2-C18alkeny), C7-C11phenylalkyl, O-phenyl, O- C7- C9phenyiaikyi or halogen. CN, COOR500, CONR500R500; Qs is CR502R503. CH=CH2. (CRsoaRsOalni CR504=CR505-CR506R507» (CR504=CR505-CR506R507)ni C=CR508R509, (C=CR508R609)n, O, C=0, NR510, NRsirC^O, 0-C(O)-0, SO2, S, SJR512R513, O- SiR5i2R5i3-0; R502, R5031 R504, R505, R506. R507, R508. R509, R510. R511, R512 and Rsia independently of each other are hydrogen, substituted or unsubstituted C1-C18alkyl, C2-C18alkenyl, C3-C18alkinyl, C3- Cycycloalkyl, phenyl, 0(C1-C18alkyl), 0(C2-C18alkeny), Cy-Cuphenylalkyl, O-phenyl, O- C7- C9phenylalkyl or halogen; n is a number from 1 to 10; y is a number from 1 to 25000 and; z is a number from 0 to 25000. Qe is a homo-, co- or tapered polymer resulting from the monomers as defined in claims 18 and 19, t is a number from 0 to 25000 and the other substituents are as defined in claim 27. 29. Use of a nitroxyl-ether containing a group (=NO-X), wherein X is selected such, that cleavage of the 0-X bond occurs and a radical X« is formed at about the melting temperature of the polymer for the preparation of a grafted polymer with and without a free radical source. 30. Use of a grafted polymer according to step A) of claim 1 or claim 2 as macroinitiator for radical polymerization. 31. Use of the polymer obtained according to the process of claiml or claim 2 as adhesive or as compatibilizer for polymer blends or as polymer toughening agent. 32. A process for the preparation of a grafted polymer snbstantially as herein described and exemplified. 33. A polymeric radical mitiator substantially as herein described aad exemplified.

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in-pct-2001-464-che-abstract.pdf

in-pct-2001-464-che-claims filed.pdf

in-pct-2001-464-che-claims granted.pdf

in-pct-2001-464-che-correspondnece-others.pdf

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in-pct-2001-464-che-description(complete)filed.pdf

in-pct-2001-464-che-description(complete)granted.pdf

in-pct-2001-464-che-form 1.pdf

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