MXPA01002255A

MXPA01002255A - Grafting of ethylenically unsaturated monomers onto polymers

Info

Publication number: MXPA01002255A
Application number: MXPA/A/2001/002255A
Authority: MX
Inventors: Nesvadba Peter; Michael Roth; Rudolf Pfaendner
Original assignee: Ciba Specialty Chemicals Holding Inc; Nesvadba Peter; 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 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 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 to a temperature at which cleavage of the nitroxyl-polymer bond occurs and polymerization of the ethylenically unsaturated monomer or oligomer is initiated at he polymer radical;maintaining said temperature for further polymerization and afterwards cooling down the mixture to a temperature below 60°C. Further subjects are grafted thermoplastic 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 thermoplastic polymers.

Description

GRAFTING OF MONOMERS ETHINICALLY INSATURED IN 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, this step comprises heating a polymer and a compound that contains a NO-ether 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, at a temperature at which cleavage of the nitroxyl-polymer linkage occurs. Additional objects of the present invention are graft polymer prepared by the process, the intermediate polymeric radical initiator, the use of the polymeric radical initiator and the use of NO-ethers to insert polymers. Increased activities have been directed towards chemical modifications of existing polymers in order to obtain new functional and / or engineering materials. Chemical modifications of existing polymers are important for at least two reasons: 1. It can be an economical and quick way to get new polymers without having to look for new monomers; 2. It can be the H | ^ -t? only way to synthesize polymers with the new intended characteristics. An important chemical modification is the grafting of free radicals of reactive monomers, which involves the reaction of a polymer with a monomer or mixture of monomers containing vinyl groups, capable of forming grafts on the polymer backbone. If the grafts are long, the modified polymer becomes a real 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, say, five portions, most of the physical and mechanical properties of the modified polymer substrate will be retained. The advantages of free radical grafting are further achieved with the use of batch mixers or screw or screw extruders, such 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, Blackie Academic & Professional a Chapman print & Hall, London 1997, chapter 1, pages 1-97. ------------------------ t ^ These free radical grafting reactions are usually performed in the presence of a source of free radicals such as a peroxide or a reactive monomer, such as, for example, acrylic acid. However, the use of free radical sources such as peroxides can cause undesired properties and leads to problems during processing (gel formation, entanglement, molecular weight reduction) or during use. Typically, long-term stability is reduced and / or the polymer can no longer be used in outdoor applications or applications at elevated temperatures. The patent of the U.S.A. 4,581,429 issued to Solomon et al., On April 8, 1986, describes a free radical polymerization process that controls the growth of polymer chains to produce oligomeric or short chain homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R'R1 'N-O-X, wherein X is a species of free radicals capable of polymerizing unsaturated monomers. Surprisingly, it has now been found that with specific compounds R'R,, N-0-X, it is possible to produce a polymeric radical initiator when grafting _. A * l ^ a! S, the group R'R "N-O in the polymer and use this macroinitiator for additional grafting reactions of olefinically unsaturated monomers. The polymerization processes and the resin products of the present invention are useful in many applications, including a variety of specialty applications, such as the preparation of graft block copolymers which are useful as compatibilizing agents for polymer blends or dispersing agents for coating systems. An object of the present invention is a process for the preparation of a graft polymer wherein in a first step: A) a stable nitroxyl radical is grafted onto a polymer, this step comprises heating a polymer and a nitroxyl ether containing a group (= N0-X), where X is chosen such that the 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 at a temperature at which cleavage of the nitroxyl-polymer link occurs and the polymerization of the monomer or oligomer is initiated ethylenically unsaturated 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 below 60 ° C, before further reaction of step B) is carried out. Optionally, a source is also present free radicals. The reaction mixture after step A) can also be cooled to a temperature lower than 60 ° C before further reaction of step B) is carried out. Preferably, the source of free radicals is a bis-azo compound, a peroxide or a hydroperoxide. Preferred specific radicals are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2, -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-methoxivaleronitrile, dimethyl-2, 2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4- 25 trimethylpentane), 2,2'-azobis (2-methylpropane) ), 2,2'- azobis (N, N '-dimet ilenisobutyramidine), free base or hydrochloride, 2'2'-azobis (2-amidinpropane), free base or hydrochloride, 2'-azobis. { 2-metí 1-N- [1, 1-bis (hydroxymethyl) ethyl] propionamide} or 2, 2 '-azobis. { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy-ethyl] propionamide; acetyl cyclohexane sulfonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, K ^ s (2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, peroxide dilauroyl, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl peroxide per 2-ethylhexanoate, 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 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, peroxide 2, 5 -dimethylhexan-2, 5-di-t-butylperoxide, 3-t-butylperoxy 3-f-enylfide, di-t-amyl peroxide, a, '-bis (t-butyl) lperoxy isopropyl) benzene, 3,5-bis (t-butylperoxy) 3, 5-dimethyl-1,2- "S ^ dioxolane, di-t-butyl peroxide, 2,5-dimethylhexin-2, 5-di-t-butyl peroxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5 -tetraoxa cyclononane, p-menthane hydroperoxide, pinano hydroperoxide, diisopropylbenzen mono-a-hydroperoxide, eumeno hydroperoxide or t-butyl hydroperoxide .. Peroxides are most preferred Examples of suitable polymers are listed 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 example of cyclopentene or norbornene, polyethylene (which can optionally be interlaced) for example high density polyethylene (HDPE = high density polyethylene), high density polyethylene and high molecular weight (HDPE-HMW = high density and high molecular weight polyethylene), high density polyethylene and ultra high molecular weight (HDPE-UHM = high density and ultrahigh molecular weight polyet hylene), medium density polyethylene (MDPE medium density polyethylene), low density polyethylene (LDPE = low density polyethylene), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially the following: a) radical polymerization (usually with high pressure and at elevated temperature). b) catalytic polymerization using a catalyst that normally contains one or more than one metal 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 already be p- or s-coordinated. These metal complexes can be in the free form or fixed in substrates, typically in activated magnesium chloride, titanium (III) chloride, alumina or 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, hydrides of - < & metal, metal alkyl halides, metal alkyl oxides, or metal alkyloxanes, the metals are elements of the groups la, lía and / or Illa of the Periodic Table. The activators may be conveniently modified with additional ester, ether, amine or silyl ether groups. These catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single-site catalysts.

(SSC = Single Site Catalysts). 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 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 copolymers / but -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 ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and blends of these copolymers with each other and with polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate (EVA) copolymers, LDPE / ethylene-acrylic acid (EAA) copolymers , LLDPE / EVA, LLDPE / EAA and random or alternating carbon monoxide / polyalkylene copolymers and their mixtures with other polymers, for example polyamides. 4. Hydrocarbon resins (for example 5-9 carbon atoms) including their hydrogenated modifications (for example tackifying agents) 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, e s t i r ene / a c r i 1 on i t r i 1, _ ^ t. E * 1iw ^ styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact strength mixtures of styrene copolymers and another polymer, 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. Copolymers of styrene graft or an α-methylstyrene, for example styrene in polybutadiene, styrene in polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile methyl methacrylate in polybutadiene, styrene and maleic anhydride in polybutadiene; styrene, acryliconitrile and maleic anhydride or maleimide in polybutadiene; styrene and maleimide in polybutadiene; styrene and alkyl acrylates or methacrylates in polybutadiene; styrene and acrylonitrile in ethylene / propylene / diene terpolymers; styrene and acrylonitrile in polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers as well as their mixtures with copolymers listed under 6), for example mixtures of copolymers 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 sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and epichlorohydrin copolymers, especially polymers of compounds of vinyl containing halogen, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or copper chloride copolymers vinylidene / vinyl acetate. 9. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified for 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, acrylonitrile / alkyl acrylate copolymers, copolymers of acrylonitrile / coxial acrylate or acrylonitrile / vinyl halide or acrylonitrile / alkyl methacrylate / butadiene terpolymers. 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or their acetals, 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 esters such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers. 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide 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 with another, as well as their precursors. 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 and / or terephthalic acid and with and 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 aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or inserted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as modified polyamides or copolyamides with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, 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 copolyether block esters derived from polyethers terminated 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 aforementioned polymers (poly blends), 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 thermoplastic. PC / PUR thermoplastic, 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). More polyethylene, polypropylene, polybutadiene, SBS and EPDM (ethylene-propylene diene monomer) are preferred. A preferred nitroxyl ether is of the formula (X) wherein nx is 0 or 1, R? oi / R? o2 R? o3 each independently of the others is hydrogen, halogen, N02, cyano, -CONR105R106, - (R109) COOR104, -C (O) -R107, -OR108, -SR108, -NHR108, -N (R108) 2, carbamoyl, di (C1-C18 alkyl) carbamoyl, -C (= NR105) (NHR106); without substituting alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom; or alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 a 12 carbon atoms containing at least one nitrogen or oxygen atom, which is replaced by ^ JÜtfJ ^ N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4) carbon atoms) amino; or phenyl which is unsubstituted or substituted by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 to 4 atoms carbon or di (C1-C4 alkyl) amino; or R102 and R103 together with the linking carbon atom form a cycloalkyl radical with 3 to 12 carbon atoms, a radical (cycloalkane with 4 to 12 carbon atoms) -yl or a cycloalkyl radical with 3 to 12 carbon atoms which contains at least one atom of 0 and / or a group NR108; or if nx is 1 R104 is hydrogen, alkyl having 1 to 18 carbon atoms, phenyl, an alkali metal cation or a tetraalkylammonium cation; R 5 and R 6 are hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms which is substituted by at least one hydroxy group or together form an alkylene bridge with 2 to 12 carbon atoms. carbon or an alkylene bridge with 2 to 12 carbon atoms interrupted by at least one atom of O or / and NR108, R107 is hydrogen, alkyl with 1 to 18 carbon atoms or phenyl, R108 is hydrogen, alkyl with 1 to 18 atoms of ca-carbon or alkyl having 2 to 18 carbon atoms which is substituted by at least one hydroxy group, R109 is alkylene with 1 to 12 carbon atoms or a direct bond, R110 is alkyl with 4 to 18 carbon atoms linked by a tertiary C atom with the nitrogen atom, phenylalkyl with 9 to 11 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom, or alkyl with 4 to 18 carbon atoms bonded by a tertiary C atom io to the nitrogen atom, phenylalkyl with 9 to 11 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom, which are substituted by N02, halogen, amino, hydroxy, cyano, carboxy alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) amino; or phenyl, naphthyl, which are unsubstituted or substituted by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 to 4 carbon atoms. at 4 carbon atoms or di (C1-C4 alkyl) amino; if n-, is 1 Rn? is alkyl having 1 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom; or alkyl with 1 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) Not me; or ^^ AíSÉg ^^ phenyl, naphthyl, which is unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy , alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) 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 Rn? together they form an alkylene bridge with 2 to 12 carbon atoms, an alkylene bridge with 3 to 12 carbon atoms or an alkylene bridge with 2 to 12 carbon atoms that is interrupted by at least one 0 or N atom, these bridges are Substituted or substituted with alkyl having 1 to 18 carbon atoms, hydroxy-alkyl having 1 to 4 carbon atoms, phenyl, phenylalkyl with 7 to 9 carbon atoms, N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms. at 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) amino, R112 is hydrogen, - (R109) COOR104 / cyano, - OR108, -SR108, -NHR108, -N (R108) 2, -NH-C (O) -R108 alkyl with 1 to 18 carbon atoms unsubstituted, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 atoms carbon "-" js.-Sjt-t.ca "phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom; or alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 a 12 carbon atoms containing at least one nitrogen or oxygen atom, which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (C1-C4 alkyl) amino; or phenyl, naphthyl, which is unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 to 4 carbon atoms, di (C 1-4 alkyl) amino; or Rm Y R? i2 together with the linking carbon atom form a cycloalkyl radical with 3 to 12 carbon atoms. Another preferred nitroxyl ether is of the formula XXa, XXb or XXc wherein 10 Y1 is O or CH2; Q is O or NR220, wherein R220 is hydrogen or alkyl with 1 to 18 carbon atoms; R201 is alkyl with 4 to 18 tertiary carbon atoms or phenyl, which is unsubstituted or substituted by Halogen, OH, COOR221 or C (O) -R222 wherein R221 is hydrogen, an alkali metal atom or alkyl having 1 to 18 carbon atoms and R222 is alkyl having 1 to 18 carbon atoms; or R201 is cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms which is interrupted by at least one O or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical that is interrupted by at least one 0 or N atom; R202 and R203 independently are alkyl with 1 to 18 carbon atoms, benzyl, cycloalkyl with 5 to 12 carbon atoms or phenyl, which are unsubstituted or iri - GÍÉHGM. - ~ -VI- T T - - '?? 'í m i -f? Substituted by halogen, OH, COOR221 or C (0) -R222 ° together with the carbon atom form a cycloalkyl ring with 5 to 12 carbon atoms; Yes, and? is O, R204 and R212 are OH, 0 (alkali metal) alkoxy with 1 to 18 carbon atoms, benzyloxy, NR223R224, wherein R223 and R224 independently of each other are hydrogen, alkyl having 1 to 18 carbon atoms or phenyl, which is unsubstituted or substituted by halogen, OH, COOR221 or C (0) -R222; if Yt is CH2, R204 is OH, alkoxy with 1 to 18 carbon atoms, benzyloxy, O-C (O) - (alkyl with 1 to 18 carbon atoms) or NR223R224; R212 are a group C (0) R225, wherein R225 is OH, alkoxy with 1 to 18 carbon atoms, benzyloxy, NR223R224, wherein R223 and R224 independently of each other are hydrogen, alkyl having 1 to 18 carbon atoms or phenyl , which are unsubstituted or replaced by halogen, OH, COOR22? or C (O) -R222; R205, R2o6 R207 and R208 independently of one another are alkyl having 1 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or phenyl; or R205 and R206 and / or R207 and R208 together with the carbon atom form a cycloalkyl ring with 5 to 12 carbon atoms; --A, ¿- * '> The radicals R209 and R2io independently are hydrogen, formyl, alkyl with 2 to 18 carboncarbonyl atoms, benzoyl, alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 atoms carbon that is interrupted by at least one 0 or N, benzyl or phenyl atom that is unsubstituted or substituted by halogen, OH, COOR221 or C (O) -R222; R2u is formyl, alkyl having 2 to 18 carboncarbonyl atoms, benzoyl, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms which is interrupted by at least one atom O or N, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR221 or C (0) -R222. Still another preferred nitroxyl ether contains a structural element of the formula (XXX) (XXX), where G1 # G2, G3, G4 independently are alkyl having 1 to 6 carbon atoms or Gx and G2 or G3 and G4, or Gx and G2 and G3 and G4 together form a cycloalkyl group with 5 to 12 carbon atoms; G5, G6 independently are H, alkyl having 1 to 18 carbon atoms, phenyl, naphthyl or a COOC-alkyl group with 1 to 18 carbon atoms. A nitroxyl ether is particularly preferred, wherein the structural element of the formula (XXX) is any of the formulas A to S [T] k coo- (G) 10 ..JL. ^^ fifteen wherein G-,, G2, G3 and G4 independently are alkyl with 1 to 4 carbon atom, or Gx and G2 together and G3 and G4 together or Gx and G2 together or G3 and G4 together are pentamethylene; G5 and G6 independently are hydrogen or alkyl with 1 to 4 carbon atoms; R, if m is 1, is hydrogen, alkyl having 1 to 18 carbon atoms 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 atom, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or a α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, wherein each carboxylic acid may be substituted in the aliphatic, cycloaliphatic, or aromatic moiety by 1 to 3 groups -COOZ12, wherein Z12 is H, alkyl with 1 to 20 carbon atoms, alkenyl with 3 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, 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 alkylene with 2 to 12 carbon atoms, alkenylene with 4 to 12 carbon atoms, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic dicarboxylic acid or aromatic having 8-14 carbon atoms or an aliphatic dicarbamic acid, cycloaliphatic or aromatic having 8-14 carbon atoms, wherein each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic portion 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 -C00Z12, 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, Rx is alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, aralkyl with 7 to 8 carbon atoms, alkanoyl with 2 to 18 carbon atoms, alkenoyl with 3 a 5 carbon atoms or benzoyl; when p is 1, R 2 is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkenyl with 2 to 8 carbon atoms unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH 2 CH (OH) -Z or of the formula -CO-Z- or -CONH-Z wherein Z is hydrogen, methyl or phenyl; or when p is 2, R2 is alkylene with 2 to 12 carbon atoms, arylene with 6 to 12 carbon atoms, xylylene, a -CH2CH (OH) CH2-0-B-0-CH2CH (OH) CH2-, where B is alkylene with 2 to 10 carbon atoms, arylene with 6 to 15 carbon atoms or cycloalkylene with 6 to 12 carbon atoms; or provided that R: is not alkanoyl, alkenoyl or benzoyl, R2 may also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or it may 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 R2 is a group and 'Kit »- < wherein 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, R 2 is 2,4,6-triazinyl; when n is 1, R3 is alkylene with 2 to 8 carbon atoms or hydroxyalkylene or acyloxyalkylene with 4 to 22 carbon atoms; or when n is 2, R3 is (-CH2) 2C (CH2-) 2; when n is 1, R 4 is hydrogen, alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 5 carbon atoms, aralkyl with 7 to 9 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, alkoxyalkyl with 2 to 6 carbon atoms, aryl with 6 to 10 carbon atoms, glycidyl, a group of the formula - (CH 2) m-C00-Q or of the formula - (CH 2) m-0- CO-Q wherein m is 1 or 2 and Q is alkyl with 1 to 4 carbon atoms or phenyl; or when n is 2, R 4 is alkylene with 2 to 12 carbon atoms, arylene with 6 to 12 carbon atoms, a group ^^^^^ ¿¿£ gJ ^ g ^ -CH2CH (OH) CH2-0-D-0-CH2CH (OH) CH2- where D is alkylene with 2 to 10 carbon atoms, arylene with 6 to 15 carbon atoms or cycloalkylene with 6 to 12 carbon atoms, or a group -CH2CH (OZ?) CH2- (OCH2CH (OZ1) CH2) 2- where Zt is hydrogen, alkyl having 1 to 18 carbon atoms, allyl, benzyl, alkanoyl with 2 to 12 carbon atoms or benzoyl; R5 is hydrogen, alkyl having 1 to 12 carbon atoms, allyl, benzyl, glycidyl or alkoxyalkyl having 2 to 6 carbon atoms; E is alkylene with 1 to 3 carbon atoms, the group -CH2CH (R8) -O- wherein R8 is hydrogen, methyl or phenyl, the group - (CH2) 3-NH- or a direct bond; R7 is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, aralkyl of 7 to 12 carbon atoms, cyanoethyl, aryl of 6 to 10 carbon atoms, the group -CH2CH (R8) -OH; or a group of the formula ^ HtMÉIttíía? ¡T? A ^ ^ or a group of the formula wherein G is alkylene with 2 to 6 carbon atoms or arylene with 6 to 12 carbon atoms and R is as defined above; or R7 is a group -E-CO-NH-CH2-OR6; R6 is hydrogen or alkyl with 1 to 18 carbon atoms; The formula (F) denotes a recurring structural unit of an oligomer wherein T is ethylene or 1, 2 -propylene, or is a repeating structural unit derived from an α-olefin copolymer with an alkyl acrylate or methacrylate; k is 2 to 100; and Rio is hydrogen, alkyl having 1 to 12 carbon atoms or alkoxy with 1 to 12 carbon atoms; T2 has the same meaning as R4; T3 and T4 independently are alkylene with 2 to 12 carbon atoms, or T4 is a group 'JÉiag ^ -, .. - * »? 39 T5 is alkylene with 2 to 22 carbon atoms, cycloalkylene with 5 to 7 carbon atoms, alkylene with 1 to 4 carbon atoms-di (cycloalkylene with 5 to 7 carbon atoms), phenylene or phenylene (alkylene with 1 to 4) carbon atoms); T6 is -NH (CH2) a-N (CH2) b-N [(CH2) c-N-] dH wherein a, b and c independently are 2 or 3, and d is 0 or 1; e is 3 or 4; Ei and E2, being different, each one is oxo or imino; E3 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl is substituted by chlorine or by alkyl with 1 to 4 carbon atoms. - ^ ^ ^ ^ ^ ^ ^ carbon, or phenylalkyl with 7 to 12 carbon atoms, or the phenyl alkyl is substituted by alkyl with 1 to 4 carbon atoms; E4 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl with 7 to 12 carbon atoms; or E3 and E4 together are polymethylene with 4 to 17 carbon atoms or the polymethylene is substituted by up to four alkyl groups with 1 to 4 carbon atoms; and E6 is a tetravalent aromatic or aromatic aliphatic radical. Additional suitable heterocyclic nitroxyl ethers are for example those mentioned in WO 98/30601 or in WO 98/44008, which are incorporated herein by reference. Alkyl with up to 20 carbon atoms for example is 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. Alkyl with 3 to 18 carbon atoms which is interrupted by one or more oxygen atoms is preferably derived from ethylene oxide or propylene oxide.

Alkyl with 3 to 18 carbon atoms interrupted by at least one 0 atom is for example -CH 2 -CH 2 -O-CH 2 -CH 3, -CH 2 -CH 2 -O-CH 3 or -CH 2 -CH 2- 0-CH2-CH2-CH2-0-CH2-CH3. It is preferably derived from polyethylene glycol. A general description is - ((CH2) a-0) bH / CH3, where a is a number from 1 to 6 and b is a number from 2 to 10. Alkenyl with 3 to 12 carbon atoms is linear or branched and example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecenyl including its isomers. Alkynyl with 3 to 8 carbon atoms, preferably is propargyl. Cycloalkyl with 5 to 12 carbon atoms is typically cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl. Cycloalkyl which is interrupted by at least one O or N atom for example is 2-tetrahydropyran-yl, tetrahydrofuran-yl, 1,4-dioxanyl, pyrrolidinyl, tetrahydrothiophenyl, pyrazolidinyl, imidazolidinyl, butyrolactone-yl, caprolactam-yl. Examples of alkali metal are lithium, sodium or potassium. Alkyl substituted by OH is typically 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl. . ?? * á »ses láÉti. | G! ^^^ Alkoxy with 1 to 18 carbon atoms eg, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. Alkyl with 1 to 18 carbon atoms substituted by alkoxy with 1 to 8 carbon atoms, preferably by alkoxy with 1 to 4 carbon atoms, in particular by methoxy or ethoxy, is typically 2-methoxyethyl, 2-ethoxyethyl, 3 -methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl. Alkyl with 1 to 18 carbon atoms substituted by di (alkyl with 1 to 4 carbon atoms) amino is preferably, for example, dimethylamino, diethylamino, 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl. and 4-diethylaminobutyl. Alkyl with 1 to 18 carbon atoms substituted by alkylamino having 1 to 4 carbon atoms is preferably, for example, methylamino, ethylamino, 2-methylaminoethyl, 2-ethylaminoethyl, 3-methylaminopropyl, 3-ethylamine or opium, 3-bu ti 1 ami nop r op i 1 o and 4-ethylaminobutyl.

Alkylthio with 1 to 4 carbon atoms is typically thiomethyl, thioethyl, thiopropyl, thioisopropyl, thiobutyl and thioisobutyl. Alkylcarbonyl having 2 to 18 carbon atoms for example is acetyl, propionyl, butyryl, pentylcarbonyl, hexylcarbonyl or dodecylcarbonyl. Phenylalkyl with 7 to 9 carbon atoms or aralkyl with 7 to 9 carbon atoms is for example benzyl, phenylethyl, phenylpropyl, a, a-dimethylbenzyl or a-methylbenzyl. Examples of alkylene bridges with 2 to 12 carbon atoms, preferably of alkylene bridges with 2 to 6 carbon atoms, are ethylene, propylene, butylene, pentylene, hexylene. Alkylene bridges with 2 to 12 carbon atoms interrupted by at least one N or 0 atom are, for example - CH2-O-CH2-CH2, - CH2-0-CH2-CH2-CH2, -CH2-0-CH2-CH2 -CH2-CH2-, -CH2-0-CH2-CH2-0-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 of cycloalkanone-ilo with 4 to 12 carbon atoms cyclopentanon-ilo, cyclohexanone-ilo or cycloheptanon-ilo.

Phenyl substituted by 1, 2 or 3, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms is typically methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, di-t-butylphenylphenyl, 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 heterocycloaliphatic ring system is hexamethylenetetramine (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 trifluoromatic acid. acetic Other suitable acids are benzoic acid, chloro-benzoic acid, methansulonic acid, ethansulonic acid, benzenesulfonic acid, p-toluenesulfonic acid, chlorbenzenesulfonic 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 1-4-hydroxyphenyl) propionyl radical. Additional examples are derived from propionic acid, lauric acid or methyl ethyl acetic acid or the other isomers of valeric acid. Examples of a cycloaliphatic carboxylic acid for example are 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 - (C-H2 :) -Si (Z ') 2Z ", where j is an integer 15 in the range of 2 to 5, and Z' and Z", independently between if they are alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms. Examples of di-, tri- and tetra-valent acids are, for example, malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, il-malonyl dibutyl, dibenzylmalonyl, butyl (3, 5-di- tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptendicarbonyl or a group of the formula rkr.r t. - - ^ - • - - fe ^^. ^^ fc ^ t ^ M »^^^ tta ^^ ^^? ^ ^ ^ ^ ^ trimellitoyl, citryl or nitriltriacetyl, butan-, 1,2,3,4-tetracarboxylic acid or pyromellitic acid. Examples of a dicarbamic acid are the hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radicals. Alkanoyl having 2 to 12 carbon atoms is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl. Alkyl substituted with hydroxyl, cyano, alkoxycarbonyl or carbamide, for example 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl. Any alkylene radicals having 2 to 12 carbon atoms are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Alkenylene having 4 to 12 carbon atoms is for example butenylene, pentenylene, hexenylene, heptenylene or nonenylene including its isomers. Arylene with 6 to 12 carbon atoms for example is, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene. Acyloxyalkylene having 4 to 22 carbon atoms for example is 2-ethyl-2-acetoxymethylpropylene. . Any alkoxyalkyl substituents with 2 to 6 carbon atoms are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl. C 1 -C 18 alkoxyloxy for example is formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy. The nitroxyl ethers of the formula (X) are known and can 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 formulas XXa, b and c are also known and can be prepared in accordance with European Patent Application No. 98810741.3. Typical examples will be given below.

The nitroxyl ethers of the formula XXX are also known and can be prepared as described in European Patent Application No. 98810531.8. In addition, 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-dipropyl-3- ethyl-2, 6- dimethyl-4-oxo-piperidine, which are intermediates for the corresponding 1-oxo and nitroxyl ether compounds. Another method for the preparation of 2,2-dimethyl-6,6-dialkyl-4-oxopiperidine is described by F. Asinger, M. Thiel, H. Baltz, Monatshefte für Chemie 88, 464 (1957) or by J. Bobbittt and collaborators in J. Org. Chem. 58, 4837 (1993). Oxidation of the piperidine compound in 1-oxo-piperidine derivatives is well known in the art and for example is described by L.B. Volodarsky, V. A. Reznikov, V.I. Ovcharenko in Synthetic Chemistry of Stable Nitroxides (Synthetic Chemistry of Stable Nitroxides), CRC Press, Boca Raton 1994. The tetramethylpiperidine precursors are partially available commercially or can be prepared according to known methods. For example, US 5 096 950 and the documents cited therein describe the preparation of the precursors. The process of oxidation and ether formation can be carried out as described above. Examples are given below. g ^ fc Preferably G1 # G2, G3 and G4 are methyl or ethyl and G5 and G6 are hydrogen or methyl. More preferably Glf G2 / G3 and G4 are methyl and G5 and G6 are hydrogen. Another preferred group of compounds are those wherein G? and G3 are ethyl and G2 and G4 are methyl, or Gx 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 alkyl with 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, phenyl, phenyl (C 7 to C 11 alkyl) , phenyl or phenyl (C 7 -C 11 alkyl) substituted by C 1 -C 12 alkyl, C 1 -C 12 alkoxy, OH, amino, C 1 -C 12 -alkylamino, dialkylamino with 1 to 12 carbon atoms, N02 or halogen, cycloalkyl with 2 to 7 carbon atoms, or a group, , wherein R 20, R 2 ?, and R 22 are hydrogen or alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, phenyl or cycloalkyl having 3 to 7 carbon atoms. More preferably X is selected from the group consisting of alkyl having 1 to 18 carbon atoms, benzyl, allyl, cyclopentyl or cyclohexyl. Particularly preferably allyl and cyclohexyl. A preferred subgroup are compounds of the structural formulas A, B, O or P, wherein 20 m is 1, R is hydrogen, alkyl having 1 to 18 carbon atoms which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid that has 2 to 18 carbon atoms, of an acid a cycloaliphatic carboxylic 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; p is 1; Ri is alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, aralkyl with 7 to 8 carbon atoms, alkanoyl with 2 to 18 carbon atoms, alkenoyl with 3 to 5 carbon atoms or benzoyl; R 2 is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkenyl with 2 to 8 carbon atoms 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. More preferred are those of structure A or B, wherein R is hydrogen, alkyl having 1 to 18 carbon atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms; Ri is alkyl having 1 to 12 carbon atoms, aralkyl having 7 to 8 carbon atoms, alkanoyl having 2 to 18 carbon atoms, alkenoyl having 3 to 5 carbon atoms or benzoyl; **, ja ^ "._ = a ^" & »aag. • R2 is alkyl with 1 to 18 carbon atoms, glycidyl, a group of the formula -CH2CH (OH) -Z or of the formula CO-Z, wherein Z is hydrogen, methyl or phenyl Another preferred subgroup is where the nitroxyl ether is a compound of the formula (X), nx is 1 Rioi is cyano, R 2 or R 3 each independently of the other are alkyl with 1 to 12 unsubstituted carbon atoms or phenyl, or R102 and R03, together with the linking carbon atom, form a cycloalkyl radical with 5 to 7 carbon atoms; at 12 carbon atoms linked via a tertiary C atom with the nitrogen atom, phenylalkyl with 9 to 11 carbon atoms or phenyl, or Rn and Rm together form an alkylene bridge with 2 to 6 carbon atoms which is unsubstituted or substituted with alkyl having 1 to 4 carbon atoms, and Rn2 is alkyl with 1 to 4 carbon atoms, A further preferred subgroup is wherein the nitroxyl ether is a compound of the formula (XXa), Y is O; R20? it is alkyl with 4 to 8 tertiary carbon atoms; _ & --_ fe-, ifo¡¿? .a ». -, - .s¡ "~ *. < * > % -. The R202 and R203 are methyl, ethyl or together with the carbon atom form a cycloalkyl ring with 5 to 6 carbon atoms; R204 is alkoxy with 1 to 2 carbon atoms; to 18 carbon atoms, benzyloxy or NR223R224, wherein R223 and R224 independently are hydrogen or alkyl having 1 to 8 carbon atoms, or of the formula (XXb), wherein Q? is O; R205, R206, R207 and R208 are independently methyl or ethyl, or @ R205 and R206 and / or R20 and R208 together with the carbon atom form a cycloalkyl ring of 5 to 6 carbon atoms; R209 and R2io independently of one another are formyl, alkylcarbonyl having 2 to 8 carbon atoms, benzoyl, alkyl having 1 to 8 carbon atoms, benzyl or phenyl; or of the formula (XXc), where Yi is 0; R205, R206, R207 and R208 independently of each other are methyl or ethyl; or R205 and R206 and / or R207 and R2oß together with the carbon atom form a cycloalkyl ring with 5 to 6 carbon atoms; R2n is formyl, alkylcarbonyl with 2 to 18 carbon atoms, benzoyl, alkyl with 1 to 18 carbon atoms, benzyl or phenyl and R212 is OH, alkoxy with 1 to 18 carbon atoms, benzyloxy, NR223R224 / where R223 and R224 are independently from each other hydrogen or alkyl having 1 to 18 carbon atoms. Preferably, the polymer to be grafted contains unsaturated portions selected from the group consisting of polydienes, block copolymer polymers, random polymers and styrene derivatives, terpolymers with diolefins and copolymers with diolefins. Preferred unsaturated polymers are polybutadiene, polyisoprene, styrene-isoprene block copolymers (SI, SIS), styrene-butadiene block copolymers (SB, SBS, SEBS), ABS, EPDM, butyl rubber, chloroprene rubber and nitrile rubber having a content of unsaturated repetitive units of 0.1 to 85%. More preferred are SB, SBS, EPDM having a content of unsaturated repeating units of 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, 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 the formula CH 2 = C (Ra) - (C = Z) -Rb; erft where Ra is hydrogen or alkyl with 1 to 4 atoms The carbon atom, Rb is NH2 / OCH3, glycidyl, unsubstituted alkoxy with 1 to 18 carbon atoms or hydroxy-substituted alkoxy with 1 to 18 carbon atoms, unsubstituted alkylamino with 1 to 18 carbon atoms, di ( alkyl with 1 to 18 carbon atoms) amino, substituted alkylamino with 1 to 18 hydroxy-substituted carbon atoms or di (alkyl with 1 to 18 carbon atoms) amino-substituted hydroxy; Me is a monovalent metal atom Z is oxygen or sulfur. More preferably Ra is hydrogen or methyl, Rb is NH2, glycidyl, unsubstituted or hydroxy substituted 1 to 4 carbon alkoxy, unsubstituted alkylamino with 1 to 4 carbon atoms, di (C1 to 4 carbon alkyl) amino, alkylamino with 1 to 4 carbon atoms or hydroxy-substituted or di (alkyl with 1 to 4 carbon atoms) amino-substituted hydroxy; and Z is oxygen. Specifically preferred ethylenically unsaturated monomers are methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, ter. butylacrylate, hydroxyethyl acrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidyl acrylates, methyla (meth) acrylate, et i (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, h i d r o x i p r o p i l (m e t) a c r i l a t, Nx ^^ '& amp; amp; amp; t-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylates, acrylonitrile, acrylamide or methacrylamide. The temperature applied in the first reaction stage depends on the polymer and for example is 50 ° to 150 ° C on the glass transition temperature (Tg) for amorphous polymers and 20 ° to 180 ° C on the melting temperature (Tm) for semi-crystalline polymers. Typical are the following temperatures: 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 ethylene-propylene-modified diene EPDM 180-260 ° C ethylene-propylene rubber EPR 180-260 ° C In a preferred process, the temperature in the first stage A) is 150 ° C to 300 ° C, more preferable from 170 ° C to 280 ° C. The temperature of preference in the second stage B) is 70 ° to 280 ° C, more preferably 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. j ^^^^^ If a temperature of 240 ° to 300 ° C is applied, the group X is preferably cyclohexyl or alkyl. The preferred compound containing a structural element of the formula (I) is present in an amount of 0.1% to 30%, more preferably in an amount of 1% to 20% and in particular in an amount of 1% to 10% based on the weight of the polymer. Preferably, the ratio of the reaction product from step A) to the ethylenically unsaturated monomer or oligomer added to step B) is 1: 10000 to 10: 1, more preferably from 1: 1000 to 1: 1 and in particular from 1: 500 to 1: 1. Step A) of the process can be carried out in any suitable reactor for mixing a polymer melt. 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 a reactive extrusion process. Examples of equipment and processes of reactive extrusion are given by G. H. Hu and collaborators, in "Reactive Modifiers for Polymers" (Reagent Modifiers for Polymers), first edition, Blackie Academic & Professional a Chapman Print & Hall, London 1997, chapter 1, pages 1-97.

Preferably, if an extruder is used, a reduced pressure of less than 200 mbar is applied during extrusion. In this way volatile by-products are 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 polymeric radical initiator at room temperature for some time. The intermediate polymeric radical initiator is stable at room temperature and no loss of activity occurs for up to several months. The reaction for step B) can be carried out in any suitable reactor for mixing a polymer melt with a monomer. The degree of grafting depends on the reaction time, the temperature used and the activity of the polymeric initiator. Preferably, the reaction time for step B) is from 1 minute to 20 hours, more preferably from 30 minutes to 5 hours.

¿¿¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡^ ^ ^^^^^^^^^^^^^^^^^^^ If the reaction step B) is carried out 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 mixtures of polymers or alloys, adhesion promoters between the two different substrates, surface modifying agents, nucleating agents, coupling agents between the filler and polymer matrix or dispersing agents. . The process is particularly useful for the preparation of block copolymers and grafted. The grafted block copolymers are for example block copolymers grafted from polystyrene 15 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 curing agents Diblock copolymers poly (methyl methacrylate-co-acrylate) or triblock copolymers poly (methacrylate-co-acrylate-methacrylate), are useful as dispersing agents for coating system , as coating additives (for example rheological agents, compatibilizers, reactive diluents) or as resin components in "- * ^ * - °" '^^. ^ R ^ ...: + *. - » .. **. ^ Ji »? #? coating (for example high solids paints), styrene graft block copolymers, (meth) acrylates and / or acrylonitrile are useful for plastics, elastomers and adhesives. In addition, graft block copolymers of this invention, wherein the grafted blocks have polar monomers in a non-polar polymer, are useful in many applications as amphiphilic or dispersing surfactants, to prepare highly uniform polymer blends. In this way, the present invention also encompasses in the synthesis, novel graft block polymers, multiple blocks, star, gradients, random, hyper-branched and dendritic. 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, treatment of paper, water treatment, electronic materials, paints, coatings, photography, ink materials, imaging materials, superabsorbants, cosmetics, products for .. • -_ £ _J_- £ Í? ... * \ • AS. M? R. hair, preservatives, biocide materials or modifiers for asphalt, leather, textiles, ceramics and wood. Because the present graft polymerization is an "active" polymerization, it can be started and stopped practically at will. In addition, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymerization in a living material. Thus, in one embodiment of this invention, once the first monomer is consumed in the initial polymerization step, then a second monomer can be added to form a second block in the growing graft polymer chain in a second step of polymerization. It is therefore possible to carry out additional graft polymerizations with the same or different one or more monomers to prepare multi-block graft copolymers. In addition, since this is a radical polymerization, graft blocks can be prepared in essentially any order. Accordingly, further objects of the present invention are a polymeric radical initiator prepared according to step A) of the process without any additional free radical source and a "" ', 4 * »-» > ¥ '** • *' • -? - initiator of polymeric radicals prepared according to step A) of the process with an additional source of free radicals. Another objective of the invention is the grafted polymers obtained according to A) and B) of the process described above. The polymeric radical initiator obtained by step A) of the above process is schematically represented in the formula (Px) (Pi), where R498 is hydrogen, substituted or unsubstituted by alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, alkynyl having 2 to 18 carbon atoms; cycloalkyl with 3 to 20 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom, which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy; alkoxy with 1 a 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) amino, 0 (alkyl with 1 to 18 carbon atoms), 0 ( alkenyl with 2 to 18 carbon atoms), phenylalkyl with 7 to 11 carbon atoms, O-phenyl, 0-phenylalkyl with 7 to 9 carbon atoms or halogen or phenyl and naphthyl which is unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) ) Not me; R499 is the stable nitroxyl radical, bound at the oxygen atom; R500 is substituted or unsubstituted by alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, phenyl, phenylalkyl with 7 to 11 carbon atoms; R50? is hydrogen, substituted or unsubstituted by alkyl having 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, phenyl, O (alkyl with 1 to 18 carbon atoms), 0 (alkenyl with 2 to 18 carbon atoms), phenylalkyl with 7 to 11 atoms •TO. ^ F ^ ^ 6e carbon, O-phenyl, O-phenylalkyl with 7 to 9 carbon atoms or halogen, CN, COOR500, CONR500R500; Q5 is CR502R503, CH = CH2, (C? ¡§? R5o3) n / / (C ° CR508R509) n, O, C = 0, NR5? 0 NR51? -C = 0, 0-C (0) -0 , S02 / S, SiR5? 2R513, 0-SiR5? 2R5? 3-0; R502 / R503 / 504 / R505 'R506, 507 / R508 / 509 / R510 / R511 / R512 and R513 independently of one another are hydrogen, substituted or unsubstituted alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms , alkynyl with 2 to 18 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, phenyl, O (alkyl with 1 to 18 carbon atoms), O (alkenyl with 2 to 18 carbon atoms), phenylalkyl with 7 to 11 carbon atoms, O-phenyl, O-phenylalkyl with 7 to 9 carbon atoms 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 R501 is H or methyl; Q5 is CR502R503, CH = CH2, wherein R502 and R503 is H, methyl or alkenyl having 2 to 9 carbon atoms 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 the formula (P2) which is obtained by step B) of the above process.

Definitions and examples of the substituents are as given above; Q6 is a homo-, co- or taper polymer resulting from the monomers described above, t is a number from 0 to 25000. R499 can be removed in thermal or chemical form. Preferably the polymer (P2) is grafted with a monomer selected from the groups described above and more preferably with styrenes, (meth) acrylates, butadiene, isoprene. * & Jft- * S- * > v More preferred 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. Examples and preferences have already been given. A further object of the present invention is the use of a nitroxyl ether containing a group (= NO-X), wherein X is chosen such that the cleavage of the bond 0-X occurs and a radical X "is formed approximately at the melting temperature of the polymer for the preparation of a grafted polymer with and without a source of free radicals. Still further objectives are the use of a grafted polymer according to step A) of the process described above as a macroinitiator for radical polymerization, and the use of the polymer obtained according to the process as an adhesive or as compatibilizer for polymer blends or as an agent for imparting resistance to the polymer. The following examples are illustrated in the invention. A) Grafting of N-OR compounds to the polymer (preparation of a polymeric initiator) Polypropylene (MFR230 / 2.16 = 1.43 according to ISO 1133) is extruded together the compound shown in Table 2 into a twin screw extruder (TW 100 from Haake, Germany) at 180-210 ° C (heating zones 1-5) and 40 rpm. The melt viscosity (MFR) is determined in accordance ISO 1133 (Table 1). The granulated polymer dissolves, reprecipitates and high-temperature NMR spectra are taken to determine if NO portions bound polymer are present. Table 1 N-OR to polypropylene grafting compound 1: l-allyloxy -4 -propoxy -2, 2,6,6-tetramethylpiperidine peroxide 1: 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane in clay (45%) * MFR according to to ISO 1133 - 5 ^ y ^^ x & ¡jj ^ y ^^ s £ B) Grafting of N-OR to the polymer and subsequent analogous reaction of commercially available SBS polymer (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 from Haake, Germany) at 180-210 ° C (heating zones 1-5) and 40 rpm. In an evacuated Schlenk reactor, purged with argon, 5 g of granular polymer are dissolved in 50-100 mL of monomer under argon atmosphere. Dissolved oxygen is removed in freeze-thaw cycles (liquid nitrogen). The reaction mixture is stirred and heated under an argon atmosphere. The remaining monomer is removed in vacuo and the residue is dried under vacuum until constant weight is achieved. Molecular weights and molecular weight distributions are determined by permeation gel permeation chromatography (GPC = Gel Permeation Chromatography). The results are illustrated in Table 3. __a_i _____ 8_í_a -___- ífc «¡^ ^ ^ ji ^ jteftfc a-aafeg ... j > < ", &;, ..- > . . 3 > w »Table 2 N-OR grafting to the polymer Compound 2: l-cyclohexyloxy-2, 2,6,6-tetramethyl-piperidin-4-yl ester of benzoic acid * bimodal distribution; peak molecular weight (Mp) for peak of MW Table 3 Analogous reaction to polymer ? tlaa 'S. "; SB .. ^^ J¿-s - Jtt * - .. - $ * bimodal distribution; peak molecular weight (Mp) from high peak MW ** tail in high MW area

Claims

CLAIMS 1. A procedure for the preparation of a grafted polymer where in a first stage: A) a stable nitroxyl radical is grafted onto a polymer, this

The step comprises heating a polymer and a nitroxyl-ether containing a group (= NO-X), wherein X is chosen such that the cleavage of the bond 0-X occurs and a radical X "is formed at about melting temperature of the polymer; and in a second stage B) the
The grafted polymer from stage A) is heated in the presence of an ethylenically unsaturated monomer or oligomer, at a temperature at which cleavage of the nitroxyl-polymer link occurs and the polymerization of the ethylenically-based monomer or oligomer is initiated. 15 unsaturated in the polymer radical; maintaining the temperature for further polymerization and subsequently cooling the mixture to a temperature below 60 ° C. 2. A process according to claim 1, characterized in that a source of free radicals is additionally present. 3. A process according to claim 2, characterized in that the source of free radicals is a bis-azo compound, a peroxide or 25 a hydroperoxide.
- «« --- - '^ -. ** X * JZ L- .. ^^ ~ - - - - _ ......-.- > «-.,.» -._- > ? ...
4. A process according to claim 3, characterized in that the source of free radicals is 2, 2'-azobisisobutyronitrile, 2,2'-azobis (2-ethyl-butyronitrile), 2,2'-azobis (2,4-dime) t-Ilevaleroni trilo), 2, 2'-azobis (4-methoxy-2,4-dimetylvaleronitrile), 1'1'-azobi s (1-cyclohexanecarbonitrile), 2,2'-azobis (isobutyramide) dihydrate, 2-f eni-loop -2, 4-dimethyl-4-methoxyvalenyl trile, di me ti 1 -2, 2'-azobisisobuterate, 2- (carbamoylazo) isobutyromethyl, 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- [l, l-bis (hydroxymethyl) ethyl] -propionamide} or 2, 2 '-azobis. { 2- m e t i l - N - [1, 1 - b? s (h i d r or x i m e t i l) -2-hydroxyethyl] propionamide; acetyl cyclohexane peroxide sulfonyl, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-am i 1 perpi va 1 ato, 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, 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- 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, '-bis (t-butylperoxy) 10 isopropyl) benzene, 3, 5-bis (t-butylperoxy) 3, 5-dimethyl-1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexin-2,5-di-t-butyl peroxide , 3, 3, 6, 6, 9, 9-hexamethyl 1, 2, 4, 5-tetraoxa-cyclononane, p-menthane-hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-a-15-hydroperoxide, hydroperoxide eumeno or hydroperoxide t- Butyl
5. A process according to claim 1, characterized in that the polymer is polyethylene, polypropylene, polystyrene, copolymers of 20 block of styrene, polybutadiene or polyisoprene, EPDM (ethylene-propylene diene monomer) or EPR (ethylene-propylene rubber).
6. A process according to claim 1, characterized in that the nitroxyl ether 25 is of the formula (X) ^^^^^^^^^^^^^^^^^^^^^^^^^^^^ X ^ s ^^^^^^^^^^^^^^ ^^^^^^^^^^^^^ X ^^^^^ ^^^^^^^^^^^^^^^^^^ wherein nx is 0 or 1, Rioi R? o2 R? o3 each independently of the others is hydrogen, halogen, N02, cyano, -CONR105R106, - (R109) COOR104, -C (O) -R107, -OR108, -SR108, -NHR108, -N (R108) 2, carbamoyl, di (alkyl having 1 to 18 carbon atoms) carbamoyl, -C (= NR105) (NHR? 05); without substituting alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom; or alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 a 12 carbon atoms containing at least one nitrogen or oxygen atom which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms k & & ^ i & l & Ssitih g * ^ carbon, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) amino; or phenyl, which is unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 to 4 carbon atoms or di (C 1 -C 4 alkyl) amino; or R102 and R103, together with the linking carbon atom form a cycloalkyl radical with 3 to 12 carbon atoms, a Radical (cycloalkanone with 4 to 12 carbon atoms) -1 or a cycloalkyl radical with 3 to 12 carbon atoms containing at least one O atom and / or a group NR? 08; or if nx is 1 Rio is hydrogen, alkyl having 1 to 18 carbon atoms, phenyl, an alkali metal cation or a tetraalkylammonium cation; R105 and R? 06 are hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms which is substituted by at least one hydroxy group or together form an alkylene bridge with 2 to 12 carbon atoms or a alkylene bridge with 2 to 12 atoms ?? . - ^ »**« aa-K? "Ar ^^^? 3ag & afo" «, ^« - gg- > a. of carbon interrupted by at least one O and / or NR108 atom; R? 07 is hydrogen, alkyl having 1 to 18 carbon atoms or phenyl; R108 is hydrogen, alkyl having 1 to 18 carbon atoms or alkyl having 2 to 18 carbon atoms which is substituted by at least one hydroxy group; Rx09 is alkyl with 1 to 12 carbon atoms or a direct bond; R110 is an alkyl with 4 to 18 carbon atoms linked via a tertiary C atom to the nitrogen atom, phenylalkyl with 9 to 11 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom; or C 4 -C 18 -alkyl linked via a tertiary C atom to the nitrogen atom, phenylalkyl with 9 to 11 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least a nitrogen or oxygen atom that is substituted by N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) amino; or phenyl, naphthyl, which are unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 at 4 carbon atoms or di (C1-C4 alkyl) amino; if nx is 1, R is alkyl with 1 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen atom or oxygen; or alkyl with 1 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) Not me; or phenyl, naphthyl, which is unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 at 4 carbon atoms or di (C1-C4 alkyl) 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 m together form an alkylene bridge with 2 to 12 carbon atoms, a bridge, alkylene with 3 to 12 carbon atoms-on or a bridge alkylene having 2 to 12 carbon atoms which is interrupted by at least one O or N atom, these bridges are unsubstituted or substituted with alkyl having 1 to 18 carbon atoms, hydroxy (alkyl with 1 to 4 5 carbon atoms) , phenyl, phenylalkyl with 7 to 9 carbon atoms, N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or di (alkyl with 1 to 4 carbon atoms) amino, R112 is hydrogen, - (R109) COOR? 04, cyano, -OR108, -SR108, -NHR108, -N (R108) 2, -NH-C (O) -R108, without substituting alkyl with 1 to 18 carbon atoms. carbon, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, cycloalkyl 15 with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom; or alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, phenylalkyl with 20 7 to 9 carbon atoms, cycloalkyl with 3 to 12 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom, which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, alkylamino with 1 at 4 carbon atoms or di (C1-C4 alkyl) amino; or phenyl, naphthyl, which is unsubstituted or substituted by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 alkylthio atoms having 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino with 1 to 4 carbon atoms, di (C1-C4 alkyl) amino; or R? and R112 together with the linking carbon atom form a cycloalkyl radical with 3 to 12 carbon atoms.
7. A method according to claim 1, characterized in that the nitroxyl ether is of the formula XXa, XXb or XXc (XXb) 15 where Yx is O or CH2; Q is 0 or NR220, wherein R220 is hydrogen or alkyl with 1 to 18 carbon atoms; R2 (n is tertiary alkyl having 4 to 18 carbon atoms or phenyl, which is unsubstituted or replaced by halogen, OH, COOR22? or C (0) -R222 wherein R221 is hydrogen, an alkali metal atom or alkyl having 1 to 18 carbon atoms and R222 is alkyl having 1 to 18 carbon atoms; or R20? is cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms 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 carbon atom. O or N; R202 and R203 are independently alkyl with 1 to 18 carbon atoms, benzyl, cycloalkyl with 5 to 12 carbon atoms or phenyl, which are unsubstituted or substituted by halogen, OH, COOR22? or C (0) -R222 or together with the carbon atom form a cycloalkyl ring with 5 to 12 carbon atoms; if Y1 is 0, R204 and R2? 2 are OH, 0 (alkali metal) alkoxy with 1 to 18 carbon atoms, benzyloxy, NR223R224, wherein R223 and R224 are independently hydrogen, alkyl with 1 to 18 carbon atoms or phenyl, which is unsubstituted or substituted by halogen, OH, C00R221 or C (0) -R222; if Yx is CH2, R204 is OH, alkoxy with 1 to 18 carbon atoms, benzyloxy, O-C (O) - (alkyl with 1 to 18 carbon atoms) or NR223R224; R212 are a group C (0) R225, wherein R225 is OH, alkoxy with 1 to 18 carbon atoms, benzyloxy, NR223R224, wherein R223 and R224 independently of each other are ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^ t ^^^^^^ ¡^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ carbon or phenyl atoms, which is unsubstituted or substituted by halogen, OH, COOR221 or C (0) -R222; R205, R206 R207 and R2oß independently of one another are alkyl having 1 to 18 carbon atoms, 5-cycloalkyl with 5 to 12 carbon atoms or phenyl; or R205 and R206 and / or R207 and R2oß together with the carbon atom form a cycloalkyl ring with 5 to 12 carbon atoms; R209 and R2? 0 independently of one another are hydrogen, formyl, alkylcarbonyl having 2 to 18 carbon atoms, benzoyl, Alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms which is interrupted with at least one O or N, benzyl or phenyl atom which is unsubstituted or substituted by halogen, OH, C00R221 or C (0) -R222; R2n, is 15 formyl, C 2 -C 18 alkylcarbon, benzoyl, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkyl which is interrupted by at least one atom of O or N, benzyl or phenyl that are 20 unsubstituted or substituted by halogen, OH, C00R221 or C (O) -R222.
8. A process according to claim 1, characterized in that the nitroxyl ether contains a structural element of the formula (XXX) (XXX), where Gi, G2, G3, G4 independently are alkyl having 1 to 6 carbon atoms or G? and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a cycloalkyl group with 5 to 12 carbon atoms; G5, G6 independently are H, alkyl having 1 to 18 carbon atoms, phenyl, naphthyl or a COO-alkyl group having 1 to 18 carbon atoms.
9. A method according to claim 8, characterized in that the structural element of the formula (XXX) is any of the formulas A to S fifteen 25 . * < *you*. Eja¿ * L ^ - > ..., .i "^ ^ ^ ¿^ ^ ^^^^ g ^^^ MütéSOCL. .. v &amp * a * J-? ? ^ i £ m fifteen 25 wherein Gx, G2, G3 and G4 independently are alkyl having 1 to 4 carbon atoms, or Gx and G2 together and G3 and G4 together or Gi and G2 together or G3 and G4 together are pentamethylene; G5 and G6 independently are hydrogen or alkyl with 1 to 4 carbon atoms; R, if m is 1, is hydrogen, alkyl having 1 to 18 carbon atoms which are uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, ** m ** áttA «» ± je - ?? * ... tt ft, -... -, ', - -. ~ l * .t ** < ? JL, Z? ^) 0 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 a carboxylic acid OI, ß- unsaturated having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, wherein each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic portion by 1 to 3 -COOZ? 2 groups wherein Z12 is H, alkyl having 1 to 20 carbon atoms, alkenyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, phenyl or benzyl; or R is a monovalent radical of a carbamic acid or a phosphorus-containing acid or a monovalent silyl radical; R, if m is 2, is alkylene with 2 to 12 carbon atoms, alkenylene with 4 to 12 carbon atoms, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic dicarboxylic acid or aromatic having 8 to 14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8 to 14 carbon atoms, wherein each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic portion by one or two groups -COOZ12; or R is a divalent radical of an acid containing phosphorus or a divalent silyl radical; R, yes • »* £ ....« ...,. .- SA J »i * & U .. *. l -. * t ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ 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 -COOZ? 2, 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; when p is 1, 2 or 3, R? is alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, aralkyl with 7 to 8 carbon atoms, alkanoyl with 2 to 18 carbon atoms, alkenoyl with 3 to 5 carbon atoms or benzoyl; when p is 1, R 2 is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkenyl with 2 to 8 carbon atoms 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 alkylene with 2 to 12 carbon atoms, arylene with 6 to 12 carbon atoms, xylylene a group -CH2CH (OH) CH2-0-B-0-CH2CH (OH) CH2- wherein B is alkylene with 2 to 10 carbon atoms, arylene with 6 to 15 carbon atoms or cycloalkylene with 6 to 12 carbon atoms; or as long as Rx is not alkanoyl, alkenoyl or benzoyl, R2 can also be a "T ^, ^ ^ .A ^ < A- i? A. , --- .... -.-...... fittrtfc. • ** .. *. divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid, or dicarbamic acid may be a -C0- group; or R- and R2 together when p is 1 may be the cyclic acyl radical of a 1,2- or 1,3-dicarboxylic or aliphatic or aromatic acid, or R2 is a group wherein T7 and T8 independently are hydrogen, alkyl having 1 to 18 carbon atoms, or T7 and T8 together are alkylene with 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3, R 2 is 2,4,6-triazinyl; when n is 1, R3 is alkylene with 2 to 8 carbon atoms or hydroxyalkylene or acyloxyalkylene with 4 to 22 carbon atoms; or when n is 2, R3 is (-CH2) 2C (CH2-) 2; when n is 1, R 4 is hydrogen, alkyl with 1 to 12 carbon atoms, alkenyl with 3 to 5 carbon atoms, aralkyl with 7 to 9 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, alkoxyalkyl with 2 to 6 carbon atoms, and ® ^ ^ & & ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ of the formula - (CH2) m -COO-Q or of the formula - (CH2) mO-CO-Q wherein m is 1 or 2 and Q is alkyl with 1 to 4 carbon atoms or phenyl; or when n is 2, R4 is alkylene with 2 to 12 carbon atoms, arylene with 6 to 12 carbon atoms, a group -CH2CH (OH) CH2-0-D-0-CH2CH (OH) CH2- wherein D is alkylene with 2 to 10 carbon atoms, arylene with 6 to 15 carbon atoms or cycloalkylene with 6 to 12 carbon atoms, or a group -CH2CH (OZi) CH2- (OCH2CH (OZ!) CH2) 2- where Zx is hydrogen, alkyl having 1 to 18 carbon atoms, allyl, benzyl, alkanoyl having 2 to 12 carbon atoms or benzoyl; R5 is hydrogen, alkyl having 1 to 12 carbon atoms, allyl, benzyl, glycidyl or alkoxyalkyl having 2 to 6 carbon atoms; Q-, is -N (R7) - or -O-; E is alkylene with 1 to 3 carbon atoms, the group -CH2CH (R8) -O- wherein R8 is hydrogen, methyl or phenyl, the group - (CH2) 3-NH- or a direct bond; R7 is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, aralkyl of 7 to 12 carbon atoms, cyanoethyl, aryl of 6 to 10 carbon atoms, the group -CH2CH (R8) -OH; or a group of the formula or a group of formula 10 wherein G is alkylene with 2 to 6 carbon atoms or arylene with 6 to 12 carbon atoms and R is as defined above; or R7 is a group -E-CO-NH-CH2-OR6; R6 is hydrogen or alkyl with 1 to 18 carbon atoms; Formula (F) denotes a recurring structural unit of an oligomer wherein T is ethylene or 1,2-propylene, or is a repeating structural unit derived from an α-olefin copolymer, with an alkyl acrylate or methacrylate; k is 2 to 100; and R10 is hydrogen, alkyl with _ ^ ¿Yy = g ^^ ^^^^ ggi á || ^^^ ¡fe¿jÉ ^ BU ^^ »^^ M £ XH ¿js & ^ y ^ & ^ fi ^ ^ 1 to 12 carbon atoms or alkoxy with 1 to 12 carbon atoms; T2 has less significance than R4; T3 and T4 are independently alkylene with 2 to 12 carbon atoms, or T4 is a group T5 is alkylene with 2 to 22 carbon atoms, cycloalkylene with 5 to 7 carbon atoms, alkylene with 1 to 4 carbon atoms-di (cycloalkylene with 5 to 7 carbon atoms), phenylene or phenylene (alkyl with 1 to 4) carbon atoms); T6 where a, b and c independently are 2 or 3, and d is 0 or 1; e is 3 or 4; Ex and E2, being different each one are oxo or imino; E3 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl is substituted by chlorine or by alkyl with 1 to 4 carbon atoms, or phenylalkyl with 7 to 12 carbon atoms, or the phenylalkyl substituted by alkyl with 1 to 4 carbon atoms; E4 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl with 7 to 12 carbon atoms; or E3 * ^ "& £ & ^ .M,"? ** ^. The polymers of EMI and E4 together are polymethylene with 4 to 17 carbon atoms, or the polymethylene substituted by up to four alkyl groups with 1 to 4 carbon atoms.; and E6 is a tetravalent aliphatic or aromatic radical.
10. A process according to claim 8, characterized in that G1 # G2, G3 and G4 are methyl and G5 and G6 are hydrogen.
11. A process according to claim 1, characterized in that X is selected from the group consisting of alkyl with 1 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, alkynyl with 3 to 18 carbon atoms, phenyl, phenyl (C 7 -C 11 alkyl), phenyl or phenyl (C 7 -C 11 alkyl) substituted by C 1 -C 12 alkyl, C 1 -C 12 alkoxy, OH, amino, alkyl -amino with 1 to 12 carbon atoms, dialkylamino with 1 to 12 carbon atoms, N02 or halogen, cycloalkyl with 2 to 7 carbon atoms, or a group \ 22 ^ 20 ^ 21 where R20, R2i, and R22 are hydrogen or alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, carbon, phenyl or cycloalkyl with 3 to 7 carbon atoms.
12. A process according to claim 11, characterized in that X is selected from the group consisting of alkyl having 1 to 18 carbon atoms, benzyl, allyl, cyclopentyl or cyclohexyl.
13. A process according to claim 9, characterized in that the nitroxyl ether is of the structural formula A, B, 0 or P, where m is 10 1, R is hydrogen, alkyl having 1 to 18 carbon atoms. 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, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms , or an O, β-unsaturated carboxylic acid having 3 to 5 carbon atoms or an aromatic carboxylic acid having 7 to 15 carbon atoms; p is 1; R? is alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, aralkyl with 7 to 8 carbon atoms, alkanoyl with 2 to 18 carbon atoms, alkenoyl with 3 to 5 carbon atoms or benzoyl; R 2 is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkenyl with 2 to 8 carbon atoms without ÉMiiiHtiiáflki ^ J- * t. ^^ fa «a. . _ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ 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, characterized in that the nitroxyl ether of structural formula A or B, wherein R is hydrogen, alkyl having 1 to 18 carbon atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms; Rx is alkyl with 1 to 12 carbon atoms, aralkyl with 7 to 8 carbon atoms, alkanoyl with 2 to 18 carbon atoms, alkenoyl with 3 to 5 carbon atoms or benzoyl; R is alkyl having 1 to 18 carbon atoms, glycidyl, a group of the formula -CH 2 CH (OH) -Z or of the formula -CO-Z, wherein Z is hydrogen, methyl or phenyl.
15. A process according to claim 6, characterized in that the nitroxyl ether is a compound of the formula (X), nx is 1, R10 is cyano; 20 R? 02 and R03 each independently of the other are without substituting alkyl with 1 to 12 carbon atoms or phenyl; or R102 and 103, together with the linking carbon atom form a cycloalkyl radical with 5 to 7 carbon atoms; R110 is an alkyl with 4 to 12 carbon atoms linked by a tertiary C atom to the nitrogen atom; l ^^^^^^ ^ ^^^ i ^^^^^? S ^ ^^^ l ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^^^^^^^^^^^^ 5 phenylalkyl with 9 to 11 carbon atoms or phenyl; or R110 and Rui together form an alkylene bridge with 2 to 6 carbon atoms which is unsubstituted or substituted with alkyl having 1 to 4 carbon atoms; and R112 is alkyl with 1 to 4 carbon atoms.
16. A process according to claim 6, characterized in that the nitroxyl ether is a compound of the formula (XXa), Y is O; R20? it is alkyl with 4 to 8 tertiary carbon atoms; R202 and R203 are methyl, ethyl or together with the carbon atom form a cycloalkyl ring with 5 to 6 carbon atoms; R204 is alkoxy with 1 to 18 carbon atoms, benzyloxy or NR223R224, wherein R223 and R22 independently of each other are hydrogen or alkyl with 1 to 8 carbon atoms; or of the formula (XXb), where Q ± is O; R205, R? O? R207 and R2os independently are methyl or ethyl; or R205 and R206 and / or R207 and R208 together with the carbon atom form a cycloalkyl ring with 5 to 6 carbon atoms; R209 and R2? 0 independently of one another are formyl, alkylcarbonyl with 2 to 8 carbon atoms, benzoyl, alkyl with 1 to 8 carbon atoms, benzyl or phenyl; or of the formula (XXc), wherein Y1 is 0; R205, R2oe 2tp and R2oa independently of each other are methyl or ethyl; or R205 and R206 and / or R207 and 208 together with the carbon atom form a cycloalkyl ring with 5 to 6 carbon atoms; R211 is ¿^^^? ^ M ^ i® ^ tSt? A formyl, alkylcarbonyl with 2 to 18 carbon atoms, benzoyl, alkyl with 1 to 18 carbon atoms, benzyl or phenyl and R212 is OH, alkoxy with 1 to 18 carbon atoms, benzyloxy, NR223R224, wherein R223 and R224 independently of each other are hydrogen or alkyl having 1 to 18 carbon atoms.
17. A process according to claim 1, characterized in that the polymer to be grafted contains unsaturated portions selected from the group consisting of polydienes, co-polymers, block copolymers, random and tared styrene, terpolymers with diolefins and copolymers with diolefins.
18. A 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, acrolein, vinyl acetate, (alkyl) acrylic acid anhydrides, acid salts (alkyl) acrylic, esters (alkyl) acrylics or (alkyl) acrylamides.
19. A process according to claim 18, characterized in that the ethylenically unsaturated monomer is styrene, α-methyl styrene, p-methyl styrene or a compound of the formula CH 2 = C (Ra) - (C = Z) -Rb, wherein Ra is hydrogen or alkyl having 1 to 4 carbon atoms, Rb is NH2, OCH3, glycidyl, alkoxy with 1 to 18 carbon atoms unsubstituted or alkoxy with 1 to 18 hydroxy-substituted carbon atoms, alkyl-amino with 1 to 18 unsubstituted carbon atoms, (C 1 -C 18 alkyl) amino, substituted hydroxy substituted 1 to 18 carbon atoms or di (C 1 -C 18 alkyl) substituted amino hydroxy; I am a monovalent metal atom, Z is oxygen or sulfur.
20. A method according to claim 1, characterized in that the temperature in 10 the first stage A) is 150 ° C to 300 ° C.
21. A method according to claim 1, characterized in that the temperature in the second stage B) is from 70 ° to 280 ° C.
22. A process according to claim 1, characterized in that the compound containing a structural element of the formula (I) is present in an amount of 0.1% to 30% based on the weight of the polymer.
23. A procedure in accordance with the Claim 1, characterized in that the ratio of the reaction product from step A) to the ethylenically unsaturated monomer or oligomer added in step B) is from 1: 10000 to 10: 1. - ^^ '- -' - ---- * - '--- »- iWHm-? -m - * - .'--« - J --- »^^.-T-Aví .- ^ -? iáím? a * áí? i a- * H iiH '
24. A method according to claim 1, characterized in that the first stage A) is carried out in an extruder.
25. A polymeric radical initiator that is obtained according to step A) of claim 1 or claim 2.
26. A polymer that is obtained according to steps A) and B) of the process of claim 1 or Claim 2.
27. A polymeric radical initiator of the formula (Pl) wherein R498 is hydrogen, substituted or unsubstituted by alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, alkynyl having 2 to 18 carbon atoms; cycloalkyl with 3 to 20 carbon atoms or cycloalkyl with 3 to 12 carbon atoms containing at least one nitrogen or oxygen atom, or cycloalkyl with 3 to 12 carbon atoms containing at least one atom of nitrogen or oxygen, which is substituted by N02, halogen, amino, hydroxy, cyano, carboxy; alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylamino with 1 to 4 carbon atoms or 5 di (alkyl with 1 to 4 carbon atoms) amino, 0 (alkyl with 1 to 18 carbon atoms) carbon), O (alkenyl with 2 to 18 carbon atoms), phenylalkyl with 7 to 11 carbon atoms, O-phenyl, O-phenylalkyl with 7 to 9 carbon atoms or halogen or phenyl and naphthyl which is 10 is substituted or substituted by alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogen, cyano, hydroxy, carboxy, alkylamino having 1 to 4 carbon atoms, or (alkyl with 1 to 4 carbon atoms) amino; R499 is the 15 stable nitroxyl radical, bound at the oxygen atom; R500 is substituted or unsubstituted by alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, phenyl, phenylalkyl with 7 to 11 carbon atoms; R50 is Hydrogen, substituted or unsubstituted by C 1 -C 18 alkyl, alkenyl with 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, phenyl, 0 (alkyl with 1 to 18 carbon atoms), O (alkenyl with 25 2 to 18 carbon atoms), phenylalkyl with 7 to 11 atoms i ^ ^ -? r ^ g ^^ a -10 * carbon, O-phenyl, O-phenylalkyl with 7 to 9 carbon atoms or halogen, CN, COOR500 / CONR500R5oo; Qs is CRso2R5? 3 CH = CH2, (CR502R503) n, CR50 = CR505-CR506R50, (CR5o = CR5o5-CR506R5o7) n, C = CR508R5o9í (C = CR508R509) n, 0, C = 0, NR510, NR511-C = 0, OC (O) - 0, S02, S, S? R512R5? 3, 0-S? R512R513-0; 502 R503 50505506 R507, R508, 509, R5io R5i ?, si2 and si3 independently are hydrogen, substituted or unsubstituted alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, alkynyl with 2 to 18 carbon atoms, 10 cycloalkyl having 3 to 7 carbon atoms, phenyl, 0 (alkyl having 1 to 18 carbon atoms), O (alkenyl having 2 to 18 carbon atoms), phenylalkyl of 7 to 11 carbon atoms, O-phenyl, 0 - phenylalkyl with 7 to 9 carbon atoms or halogen; n is a number from 1 to 10; 15 and is a number from 1 to 25000 and; z is a number from 0 to 25000.
28. A polymer of the formula (P2) [P9) where ¡F ^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Q6 is a homo- polymer, co- or polymer or tapered polymer resulting in 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 (= N0-X), wherein X is chosen such that the cleavage of the OX bond occurs and is forms a radical X-approximately at the melting temperature of the polymer for the preparation of a grafted polymer with and without a source of free radicals.
30. Use of a grafted polymer according to step A) of claim 1 or claim 2, as a macroinitiator for radical polymerization.
31. 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 a polymer curing agent. '^ ^^^^^ &? ^^ Loé SUMMARY OF THE INVENTION 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, this step comprises heating a polymer and a nitroxyl ether containing a group (= NO-X), wherein X is chosen such that the cleavage of the bond 0-X occurs and a radical X- is formed at about melting temperature of the polymer; and in a second step B) the grafted polymer of step A) is heated in the presence of a monomer or ethylenically unsaturated oligomer, a temperature at which cleavage of the nitroxyl-polymer occurs, and polymerizing the monomer or oligomer ethylenically unsaturated initiates in the polymer radical; maintain the temperature for further polymerization and then cool the mixture to a temperature below 60 ° C. Additional targets are grafted thermoplastic polymers that are prepared by the process, the intermediate polymeric radical initiator, the use of the polymeric radical initiator and the use of NO-ethers to graft thermoplastic polymers. ^ S? ^? ^ i? ^^ s mm ^? áai • ^^ 8 ^ te ^^^ te ^ a ^^