Title of Invention	PROCESS FOR PREPARING AN OLIGOMER, COOLIGOMER, A POLYMER OR A COPOLYMER
Abstract	The present invention relates to a controlled free radical polymerization process in the presence of 1-alkoxy-polyalkyl-piperidine derivatives. In an alternative controlled free radical polymerization process the intermediate N-oxyl derivatives together with a source of free radicals are used.

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The present invention relates to a process for polymerizing ethylenlcally unsaturated monomers, and the use of 1-alkoxy-polyalkyi piperidine derivatives for controlled polymerization. The intermediate N-oxyi derivatives, a composition of the N-oxyl derivatives with ethylenlcally unsaturated monomers and a free radical initiator X. The compounds of the present invention provide polymeric resin products having low polydispersity. The polymerization process proceeds with enhanced monomer to polymer conversion efficiency. In particular, this invention relates to stable free radical- mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, muitiblock copolymers, graft copolymers and the like, at enhanced rates of polymerization and enhanced monomer to polymer conversions. Polymers or copolymers prepared by free radical polymerization processes inherentiy have broad molecular weight distributions or polydispersities which are G6nerally higher than about four. One reason for this is that most of the free radical initiators have half lives that are relatively long, ranG1ng from several minutes to many hours, and thus the polymeric chains are not ail initiated at the same time and the initiators provide growing chains of various lengths at any time during the polymerization process. Another reason is that the propagating chains in a free radical process can react with each other in processes known as combination and disproportionation, both of which are irreversibly chain-terminating reaction processes. In doing so, chains of varying lengths are terminated at different times during the reaction process, resulting in resins consisting of polymeric chains which vary widely in length from very small to very larG6 and which thus have broad polydispersities. If a free radical polymerization process is to be used for producing narrow molecular weight distributions, then all polymer chains must be initiated at about the same time and termination of the growing polymer-chains by combination or disproportionation processes must be avoided. Conventional radical polymerization reaction processes pose various significant problems, such as difficulties in predicting or controlling the molecular weight, the polydispersity and the modality of the polymers produced. These prior art polymerization processes produce polymers having broad polydispersities and in some instances, low polymerization rates . Furthermore, free radical polymerization processes in bulk of the prior art are difficult to control because the polymerization reaction is strongly exothermic and an efficient heat removal in the highly viscous polymer is mostly impossible. The exothermic nature of the prior art free radical polymerization processes often severely restricts the concentration of reactants or the reactor size upon scale-up. Due to the above mentioned uncontrollable polymerization reactions, G6l formation in conventional free radical polymerization processes are also possible and cause broad molecular weight distributions and/or difficulties during filtering, drying and manipulating the product resin. US-A-4 581 429 to Solomon et al., issued April 8,1986, discloses a free radical polymeriza¬tion process which controls the growth of polymer chains to produce short chain or oligo-meric homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R"R" N-O-X, where X is a free radical species capable of polymerizing unsaturated monomers. The reactions typically have low conversion rates. Specifically mentioned radical R"R"N-O groups are derived from 1,1,3,3 tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6 tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine or di-t-butylamine. However, the sugG6sted compounds do not fulfill all ^ requirements. Particularly the polymerization of acrylates does not proc^eec^fast eriough and/or the monomer to polymer conyersion is not as high as desired. Recently other attempts to develop new polymerization regulators have been published. WO 98/4408 and WO 98/30601 disclose heterocyclic compounds suitable for controlled polymerization processes. WO 98/13392 discloses open chain alkoxyamines which are derived from NO gas or from nitroso componds. EP-A-J735g52 discloses a method for preparing thermoplastic polymers of narrow poly¬dispersities by free radical-initated polymerization, which comprises adding a free radical initiator and a stable free radical aG6nt to the monomer compound. This method has the disadvantaG6 that uncontrollable recombinations of initiator radicals may occur immediately after their formation, thus producing variable ratios between initiator radicals and stable free radicals. Consequently in some cases there is no good control of the polymerization process. There is therefore still a need for polymerization processes for the preparation of narrow polydispersity polymeric resins with defined molecular weights using the economical free radical polymerization techniques. These polymerization processes will also control the /physical properties of the polymers such as viscosity, hardness, G6l content, processability, clarity, high gloss, durability, and the like. The polymerization processes and resin products of the present invention are useful in many applications, including a variety of specialty applications, such as for the preparation of block copolymers which are useful as compatibilizing aG6nts for polymer blends, or dispersing aG6nts for coating systems or for the preparation of narrow molecular weight resins or A^^^ oligomers for use in coating technoloG1es and thermoplastic films or as toner resins and liquid immersion development ink resins or ink additives used for electrophotographic " imaG1ng processes. Surprisingly, it has now been found that it is possible to overcome the afore mentioned shortcomings of the prior art by providing a polymerizable composition containing specifjc initiator compounds. Polymerization of the composition results in a polymer or copolymer of narrow polydispersity and a high monomer to polymer conversion even at relatively low temperatures and at short reaction times, making the polymerization process particularly suitable for industrial applications. The resulting copolymers are of high purity and in many cases colorless, therefore not requiring any further purification. One object of the present invention is to provide a 1-alkoxy-polyalkyl-piperidine derivative containing a structural element of formula (\) G1, Ga, G3, G4 are independently C1-C6alkyI with the proviso that at least one is not methyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 toG6ther form a C5-C12cycloalkyI group; G5, G6 independently are H, CrCiaalkyl, phenyl, naphthyl or a group COOC1-C18alkyI and X represents a group having at least one carbon atom and is such that the free radical_X5_— derived from X is capable of initiating polymerization of ethylenically unsaturated monomers, with the proviso that compounds A1 and A2 are excluded The alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl. C5-C12cycloalkyi is typically, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl. Preferred compounds or mixture of compounds are any of formulae A to S. wherein G1, G2, G3 and G4 are independently all G3 and G4 toG6ther, or G1 and G2 toG6ther or G3 and G4 toG6ther are pentamethylene; G5 and G6 are independently hydroG6n or C1-C4 alkyl; R, if m is 1, is hydroG6n, C1-C18alkyl which is uninterrupted or Ca-Ciealkyl which is interrupted by one or more oxyG6n atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ12 groups, in which Ziais H, C1-C20aikyI, C3-C12alkenyl, C5-C7cycloall R, if m is 2, is C2J^i2alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ12 groups; or R is a divalent radical of^ajjhosphorus-containing acid or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZ12, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, R, if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; p is 1, 2 or 3, ( Rj"is C2-C18alkyI, C5-C7cycloalkyl, C7-C8aralkyI, C2-C18alkanoyl, C3-C5alkenoyI or benzoyl; when p is 1, R2 Is C1-C18alkyl, C5-C7cycloalkyl, C2-C6alkenyl 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 hydroG6n, methyl or phenyl; or when p is 2, R2 isC8-C12alkylene,C8-C12arylene, xylylene, a -CH2CH(OH)CH2-0-B-0-CH2CH(OH)CH2-group, wherein B is C2-C10alkylene, Ce-Cisarylene or C6-C12cycloalkylene; or, provided that Ri is not alkanoyl, alkenoyl or benzoyl, R2 can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO-; or Ri and R2 toG6ther when p is 1 can be the cyclic acyl radical of an aliphatic or aromatic 1,2-or 1,3-dicarboxylic acid; or R2isa group where T7 and T8 are independently hydroG6n, alkyl of 1 to 18 carbon atoms, or T7 and T8 toG6ther are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3, R2 is 2,4,6-tria2inyl; when n is 1, R3 is C3-C5-alkylene or hydroxyalkylene or C4-C22acyloxyalkylene; or when n is 2, R3 is (-CH2)2C(CH2-)2; when n is 1, R4 is hydroG6n, C1-C12alkyl, C3-C5alkenyl, C7-C9aralkyi, C5-C7cycloalkyi, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, Ce-Cioaryl, glycidyl, a group of formula -(CH2)m-COO-Q or of the formula - (CH2)m-0-CO-Q wherein m is 1 or 2 and Q is C1-C4alkyl or phenyl; or when n is 2, R4 is C2-C12alkylene, C6-C12arylene, a group -CH2CH(OH)CH2-0-D-0-CH2CH(OH)CH2- wherein D is C2-C10alkyiene, Ce-Cisarylene or C6-C12cycioalkylene, or a group - CH2CH(OZi)CH2-(OCH2CH{OZi)CH2)2- wherein Zi is hydroG6n, C2-C18alkyI, allyl, benzyl, C2- C12alkanoyl or benzoyl; R5 is hydroG6n, C1-C12alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl; Gff is -NCRy)- or -0-; E is Ci-Caalkylene, the group -CH2CH(R8)-0- wherein Rais hydroG6n, methyl or phenyl, the group -(CH2)3-NH- or a direct bond; R7 is CrCiealkyI, C5-C7-cycloalkyI, C7-C12aralkyl, cyanoethyl, Ce-Cio-aryl, the group - CH2CH(R8)-OH; or a group of the formula wherein G is C2-C6alkylene or C6-C12aryiene and R is as defined above; or R7 is a group -E-CO-NH-CH2-OR6; R6 is hydroG6n or C1-C18alkyl; Formula (F) denotes a recurring structural unit of a oligomer where T is ethylene or 1,2- propylene, or is a repeating structural unit derived from an a-olefin copolymer with an alkyl acrylate or methacrylate; j Rio is hydroG6n, C1-C12alkyI or C2-C18alkoxy; T2 has the same meaning as R4; T3 and T4 are independently alkylene of 2 to 12 carbon atoms, or T4 is a group 13 T5 is C2-C22alkylene, C5-C7cycloalkylene, C1-C4alkylenedi{C5-C7cycloall where a, b and c are independently 2 or 3, and d is 0 or 1; e is 3 or 4; Ty and Ta are independently hydroG6n C1-C18alkyl, or T7 and TB toG6ther are C4-C6alkylene or 3-oxapenthamethylene; El and E2, being different, each are -CO- or -N(E5)-, where E5 is hydroG6n, C2-C18alkyI or C4-Caaalkoxycarbonylalkyl; E3 is hydroG6n, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, said phenyl or said naphthyl substituted by chlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyi of 7 to 12 carbon atoms, or said phenylalkyi substituted by alkyl of 1 to 4 carbon atoms; E4 is hydroG6n, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyi of 7 to 12 carbon atoms; or E3 and E4 toG6ther are polymethylene of 4 to 17 carbon atoms, or said polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms; and Ee is an aliphatic or aromatic tetravalent radical. C2-C18alkenyl is for example propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, dodecenyl including their isomers. C7-C9aralkyI is for example benzyl, phenylpropyl, a,a-dimethylben2yl or a-methylbenzyl. C2-C18alkyl interrupted by at least one O atom is for example -CH2-CH2-O-CH2-CH3, -CH2-CH2-O-CH3 or -CH2-CH2-O-CH2-CH2-CH2-O-CH2-CH3. It is preferably derived from polyethlene glycol. A G6neral description is -((CH2)a-O)b-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10. If R is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyi, stearoyi, acryloyi, methacryloyi, benzoyl or |3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical. If R is a mpnoya|enlsi|yLradi is, for example, a radical of the formula -(CjH2j)-Si(Z")2Z", in which j is an inteG6r in the ranG6 from 2 to 5, and Z" and Z", independently of one another, are C1-C4alkyl or C1-C4alkoxy. If R is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyi, suberoyi, sebacoyi, maleoyi, itaconyl, phthaloyi, dibutylmalonyl, dibenzylmalonyl, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical or a group of the formula ]fJR is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyi, citryl or nitrilotriacetyl radical. JfJRis atetravsilent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid. If R is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyi or 2,4-toluylenedicarbamoyl radical. C1-C18alkanoyl is for example, formyl, propionyl, butyryl, octanoyi, dodecanoyi but preferably acetyl and C3-C5alkenoyi is in particular acryloyl. Any C2-C12alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene. Any Ce-Cisarylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4"-diphenylene. C6-C12cycloalkylene is, in particular, cyclohexylene. Hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted C1-C4alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl. Any C2-C6alkoxyalkyI substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl. Preferably G6 is hydroG6n and G5 is hydroG6n or C1-C4alkyl. Preferably G1, Gg, G3 and G4 are independently C1-C4alkyl, with the proviso that at least one is different from methyl. More preferred G1 and G3 are methyl and G2 and G4 are ethyl or propyl. In another preferred group of compounds G1 and G2 are methyl and G3 and G4 are ethyl or propyl. Preferably X is selected from the group consisting of -CHa-aryl, -CHa-CHg-aryl, , (C5-C6cycloalkyOsCCN, (C1-C12alky)2CCN, - CH2CH=CH2, (C1-C12)alkyl-CR2o-C(OHC1-C12)alkyl, (C1-C12)alkyl-CR2o-C(0)-(C6-Cio)aryl, (C1-C12)alkyl-CR20-C{O)-(C1-C12)alkoxy, (C1-C12)alkyl-CR2o-C(0)-phenoxy, (C1-C12)alkyl-CR2o-C(0)-N-di(C1-C12)alkyl, (C1-C12)alkyl-CR2o-CO-NH(C1-C12)alkyl, (C1-C12)alkyl-CR2o-CO-NH2, - CH2CH=CH-CH3, -CH2-C(CH3)=CH2, -CH2-CH=CH-phenyl, R20 is hydrogen or C1-C12alkyl; the aryl groups are phenyl or naphthyl which are unsubstltuted or substituted with Ci-C12alkyl, halogen, C1-C12alkoxy, C1-C12alkylcarbonyl, glycidyloxy, OH, -COOH or -COOCr C12alkyl. More preferred are compounds, wherein X is sejected from the group consisting -CH2-phenyl, CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, -CH2CH=CH2, CH3CH-CH=CH2 (C1-C8alkyl)CR20-C(O)-phenyl, (C1-C8)alkyl-CR20-C(0)-(Ci-C8)alkoxy, (C1-C8)alkyl-CR20-C(O)-(C1-C8)alkyl, (C1-C8)alkyl-CR20-C(O)-N-di(C1-C8)alkyl, (d-C8)alkyl-CR20-C(O)-NH(C1-C8)alkyl,(C1-C8)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-C8)alkyl. Particularly preferred are compounds, whereinJ In a preferred group of compounds X contains no open chain alkylether group. Preferred compounds are those of formula A, B, O or P, particularly preferred of formula A, B or O and more preferred of formula A or B, wherein the substltuents have the meanings as defined before. A preferred group of compounds are those of formula A, B or O, wherein m is 1, R is hydroG6n, C1-C18alkyl which is uninterrupted or interrupted by one or more oxyG6n atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; pisi; Ri is C1-C12alkyl, C5-C7cycloalkyI, C7-C8aralkyl, C2-C18alkanoyI, C3-C5alkenoyI or benzoyl; R2 is C1-C18alkyI, C5-C7cycioalkyl, C2-C8alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH(OH)-Z or of the formula -CO-Z or -CONH-Z wherein Z is hydroG6n, methyl or phenyl. Amongst the group of compounds of formula A, B or O those are more preferred, wherein R is hydroG6n, C1-C18alkyI, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, carboxylic acid; Ri is C1-C12alkyl, C7-C8aralkyl, C2-C18alkanoyl, C3-C5alkenoyI or benzoyl; R2 is C1-C18alkyI, glycidyl, a group of the formula -CH2CH(0H)-Z or of the formula -CO-Z, wherein Z is hydroG6n, methyl or phenyl. A further preference for this subgroup is that G6 is hydroG6n and G5 is hydroG6n or Ci-C4alkyl, G1 and G3 are methyl and Ga and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl. In addition for the compounds of formula A, B or O a preferred group X is selected from the group consisting of -CH2-phenyl, CHaCH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, -CH2CH=CH2, CHsCH-CHziCHz, (C1-C4alkyl)CR2o-C(0)-phenyl, (C1-C4)alkyl-CR20-C(O)-(C1-C4)alkoxy, (C1-C4)alkyl-CR20-C(O)-(C1-C4)alkyl, (C1-C4)alkyl-CR2o-C(0)-N-di(C1-C4)alkyl, (C1-C4)alkyl-CR20-C(O)-NH(C1-C4)alkyl, (C1-C4)alkyl-CR20-C(O)-NH2, wherein R20 is hydroG6n or (C1-C4)alkyl. Most preferred are the compounds of formula (A), wherein G5 and G6 are hydroG6n or methyl, G1 and G3 are methyl and G2 and G4 are ethyl or G1 and G2 are methyl and G3 and G4 are ethyl; m Is 1; R is hydroG6n, C2-C18alkyI or a group -C(0)-(C2-C18)alkyl; and X is -CHz-phenyi, CHaCH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, -CH2CH=CH2, CH3CH-CH=CH2 (C1-C4alkyi)CR2o-C(0)-phenyl, (C1-C4)alkyl-CR2o-C(0)-(Cr C4)alkoxy, (Ci-G4)alkyl-CR20-C(O)-(C1-C4)alkyl, (C,-C4)alkyl-CR20-C(O)-N-di(C1-C4)alkyl, (d- C4)alkyl-GR20-C(O)-NH(C1-C4)alkyl,(C1-C4)alkyl-CR20-C(O)-NH2, wherein R20 is hydroG6n or (C1-C4)alkyl. If R is d-Ciealkyl, propyl is particularly preferred. If R is -C(0)-(C2-C18)alkyl, -C(0)-C11H23 and -C(0)-Ci7H35 are particularly preferred. A further subject of the invention is a polymerizable composition, comprising a)atleast one ethylenicaily unsaturated monomer or oligomer, and b) a 1-alkoxy-polyalkyl-piperidine derivative containing a structural element of formula (I) G1, G2, G3, G4 are independently C1-C6alkyl with the proviso that at least one is not methyl or G1 and 62 or G3 and G4, or G1 and G2 and G3 and G4 toG6ther form a C5-C12cycloalkyl group; G5, G6 independently are H, C2-C18alkyI, phenyl, naphthyl or a group COOC1-C18alkyI and X represents a group having at least one carbon atom and is such that the free radical X. derived from X is capable of initiating polymerization of ethylenicaily unsaturated monomers, with the proviso that compounds A1 and A2 are excluded Definitions for the substituents and preferred formulas fiave already been G1ven. They apply also for the composition including the preferences. Typically the ethylenically unsaturated monomer or oligomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylicacidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylo- nitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides. Preferred ethylenically unsaturated monomers are ethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene, α-C5-C18alkene, styrene, α-methyl styrene, p-methyl styrene or a compound of formula CH2=C(Ra)-(C=Z)-Rb, wherein Ra is hydroG6n or C1i-C4 alkyl, Rb is NH2, OXMe""), glycidyl, unsubstituted C1-C18alkoxy, C2-C10oalkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted C1-C18alkoxy, unsubstituted C1-C18 alkylamino, di(C1-C18alkyl)amino, hydroxy-substituted C1-C18alkylamino or hydroxy-substituted di(C1-C18alkyl)amino, -0-CH2-CH2-N(CH3)2 or -0-CH2-CH2-N*H(CH3)2 An"; An" is a anion of a monovalent organic or inorganic acid; 1 Me is a monovalent metal atom or the ammonium Ion. I Z is oxyG6n or sulfur. Examples for Ra as C2-C100 alkoxy interrupted by at least one O atom are of formula , wherein Re is C1-C25 alkyI, phenyl or phenyl substituted by C1- C18 alkyl, Rd is hydroG6n or methyl and v is a number from 1 to 50. These monomers are for example derived from non ionic surfactants by acrylation of the corresponding alkoxylated alcohols or phenols. The repeating units may be derived from ethylene oxide, propylene oxide or mixtures of both. Further examples of suitable acrylate or methacrylate monomers are G1ven below. and Ra have the meaning as defined above and Re is methyl or benzyl. An" is preferably CI", Br" or "O3S-CH3. Preferably Ra is hydrogen or methyl, Rb is NH2, gycidyl, unsubstituted or with hydroxy substituted C1-C4alkoxy, unsubstituted C1-C4alkylamino, di(C1-C4alkyl)amino, hydroxy-substituted C1-C4alkylamino or hydroxy-substituted di(C1-C4alkyl)amino;and Z is oxygen. Particularly preferred ethylenically unsaturated monomers are styrene, methylacrylate, ethylacrylate, butylacrylate, Isobutylacrylate, tert. butylacrylate, hydroxyethylacryiate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylamlnoethyl(meth)acrylate, glycldyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl-methacrylamide. Preferably the initiator compound is present in an amount of from 0.01 mol-% to 30 mol-% , more preferably in an amount of from 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture. When monomer mixtures are used mol% is calculated on the average molecular weight of the mixture. Another subject of the present invention is a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of an initiator compound containing a structural element of formula (I) under reaction conditions capable of effecting scission of the 0-C bond to form two free radicals, the radical -X being capable of initiating polymerization. Preferably scission of the O-C bond is effected by ultrasonic treatment, heating or exposure to electromagnetic radiation, ranging from y to microwaves. More preferably the scission of the O-C bond is effected by heating and takes place at a temperature of between 50°C and 160°C. The process may be carried out in the presencejof an organic solvent or in the presence of water or in mixtures of organic solvents and water. Additional cosolvents or surfactants, such as glycols or ammonium salts of fatty acids, may be present. Other suitable cosolvents are described hereinafter. Preferred processes use as little solvents as possible, In the reaction mixture it is preferred to use more than 30% by weight of monomer and initiator, particularly preferably more than 50% and most preferrably more than 80%. If organic solvents are used, suitable solvents or mixtures of solvents are typically pure alkanes (hexane, heptane, octane, isooctane), hydrocarbons (benzene, toluene, xylene), fialogenated hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether), or mixtures thereof. The aqueous polymerization reactions can be supplemented with a water-miscible or hydrophilic cosolvent to help ensure that the reaction mixture remains a homogenep,us single phase throughout the monorner conversion. Any water-soluble or water-miscible cosolvent may be used, as long as the aqueous solvent medium is effective in providing a solvent system which prevents precipitation or phase separation of the reactants or polymer products until after all polymerization reactions have been completed. Exemplary cosolvents useful in the present invention may be selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyI pyrrolidinones, N-alkyI pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxyether derivatives such as butyl carbitol or celiosolve, amino alcohols, ketones, and the like, as well as derivatives thereof and mixtures thereof. Specific examples include methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, and other water-soluble or water-miscible materials, and mixtures thereof. When mixtures of water and water-soluble or water-miscible organic liquids are selected as the aqueous reaction media, the water to cosolvent weight ratio is typically in the range of about 100:0 to about 10:90. The process is particularly useful for the preparation of block copolymers. Block copolymers are, for example, block copolymers of polystyrene and polyacrylate (e.g., poiy(styrene-co-acrylate) or poly(styrene-co-acrylate-co-styrene). They are usefull as adhesives or as compatlbilizers for polymer blends or as polymer toughening aG6nts. Poly(methylmethacrylate-co- acrylate) diblock copolymers or poly(methylacrylate-co-acrylate-co-methacrylate) triblock copolymers) are useful as dispersing aG6nts for coating systeme, as coating additives (e.g. rheoloG1cal aG6nts, compatlbilizers, reactive diluents) or as resin component in coatings(e.g. high solid paints) Block copolymers of styrene, (meth)acrylates and/or acrylonitrile are useful for plastics, elastomers and adhesives. Furthermore, block copolymers of this invention, wherein the blocks alternate between polar monomers and non-polar monomers, are useful in many applications as amphiphilic surfactants or dispersants for preparing highly uniform polymer blends, he (co)polymers of the present invention may have a number averaG6 molecular weight om 1 000 to 400 000 g/mol, preferably from 2 000 to 250 000 g/mol and, more preferably, om 2 000 to 200 000 g/mol. When produced in bulk, the number averaG6 molecular weight lay be up to 500 000 (with the same minimum weights as mentioned above). The number veraG6 molecular weight may be determined by size exclusion chromatography (SEC), G6l ermeation chromatography (GPC), matrix assisted laser desorption/ionization mass Dectrometry (MALDI-MS) or, if the initiator carries a group which can be easily distinguished om the monomer(s), by NMR spectroscopy or other conventional methods. he polymers or copolymers of the present invention have preferably a polydispersity of from 0 to 2, more preferably of from 1.1 to 1.9 and most preferably from 1.2 to 1.8. 1US, the present invention also encompasses in the synthesis novel block, multi-block, star, adient, random, hyperbranched and dendritic copolymers, as well as graft or copolymers. ie polymers prepared by the present invention are useful for following applications: ihesives, deterG6nts, dispersants, emulsifiers, surfactants, defoamers, adhesion pro-oters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, thickeners, osslinkers, paper treatment, water treatment, electronic materials, paints, coatings, photo-aphy, ink materials, imaG1ng materials, superabsorbants, cosmetics, hair products, preser-itives, biocide materials or modifiers for asphalt, leather, textiles, ceramics and wood. Because the present polymerizaton is a "living" polymerization, it can be started and stopped practically at wjll Eurtherrriore, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymerization in a living.matter. Thus, in one embodiment of :his invention, once the first monomer is consumed in the initial polymerizing step a second Tionomer can then be added to form a second block on the growing polymer chain in a second polymerization step. Therefore it is possible to carry out additional polymerizations with the same or different monomer(s) to prepare multi-block copolymers, furthermore, since this is a radical polymerization, blocks can be prepared in essentially any )rder. One is not necessarily restricted to preparing block copolymers where the sequential )olymerizing steps must flow from the least stabilized polymer intermediate to the most stabilized polymer intermediate, such as is the case in ionic polymerization. Thus it is )ossible to prepare a multi-block copolymer in which a polyacrylonitrile or a poly(meth)-icrylate block is prepared first, then a styrene or butadiene block is attached thereto, and so )n. urthermore, there is no linking group required for joining the different blocks of the present )lock copolymer. One can simply add successive monomers to form successive blocks. plurality of specifically designed polymers and copolymers are accessible by the present ivention, such as star and graft (co)polymers as described, inter alia, by C. J. Hawker in nG6w. Chemie, 1995, 107, paG6s 1623-1627, dendrimers as described by K. Matyaszewski it al. in Macrmolecules 1996, Vol 29, No. 12, paG6s 4167-4171, graft (co)polymers as lescribed by C. J. Hawker et al. in Macromol. Chem. Phys. 198,155-166(1997), random opolymers as described by C. J. Hawker in Macromolecules 1996, 29, 2686-2688, or liblock and triblock copolymers as described by N. A. Listigovers in Macromolecules 1996, 9, 8992-8993. further subject of the present invention is a polymer or oligomer, having attached at least ne initiator group -X and at least one oxyamine group of formula (la) obtainable by the above described process. The compounds of formula (I) may be prepared from the corresponding nitroxides, which are therefore intermediates for the compounds of formula (I). Therefore still another subject of the present invention is a 1 -oxy-polyalkyl-piperidine derivative containing a structural element of formula (II) G1, G2, G3, G4 are independently C1-C6alkyl with the proviso that at least one is not methyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 toG6ther form a C5-C12cycloalkyI group; G5, G6 independently are H, C1-C18alkyI, phenyl, naphthyl or a group COOC1-C18alkyI, with the proviso that compounds B1, B2 and B3 are excluded Definitions for the substituents as well as their preferences have already been G1ven. They apply also for the compounds of formula (II). In particular the corresponding formulas (A) to (S) and their preferred meanings are also preferred for the respective N-oxyls. Also subject of the present invention is a polymerizable composition, comprising a) at least one ethylenically unsaturated monomer or oligomer, and b) a compound of formula (II) and c) a radical iniator X. capable of initiating polymerization of ethylenically unsaturated monomers. The production of C-centered radicals X. is described, inter alia, in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a, paG6s 60-147. These methods can be applied in G6neral analogy. The source of radical/x»^ay be a bis-azo compound, a peroxidepr a hydroperoxide. Preferably, the source of radicals X. is 2,2"-azobisisobutyronitrile, 2,2"-azobis(2-methyl-butyronitrile), 2,2"-azobis(2,4-dimethylvaleronitrile), 2,2"-azobis(4-methoxy-2,4-dimethylva!e-ronitrile), 1,1"-azobis(1-cyclohexanecarbonitrile), 2,2"-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2"-azobisisobutyrate, 2-(carbamoytazo)isobutyronitrile, 2,2"-azobis(2,4,4-trimethylpentane), 2,2"-azobis(2-methylpropane), 2,2"-azobis(N,N"-dimethyleneisobutyramidine), free base or hydrochloride, 2,2"-azobis(2-amidinopropane), free base or hydrochloride, 2,2"-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2"-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide. Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyi peroxide, didecanoyi peroxide, dioctanoyi peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyi peroxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, a, a"-bis(t-butylperoxy isopropyl) benzene, 3,5-bis (t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexyne- 2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide. These compounds are commercially available. If more than one radical source is used, a mixture of substitution patterns is obtainable. The radical source is preferably present in an amount of from 0.01 mol-% to 30 mol-% , more preferred in an amount of from 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture. The molar ratio of the radical source to the compound of formulae II may be from 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferably from 1:2 to 2:1. Still another subject of the present invention is a process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer/oligomer, which comprises subjecting the above composition to heat or actinic radiation. Definitions and preferences for the various substituents have already been mentioned with respect to the initiator compounds. They apply also for the other subjects of the invention including the preferences. The initiators containing a structural element of formula I may be prepared by known methods. DE26 21 841, US 4M31"599"ard"DE_216 30 798 for example describe the preparation of 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidineand2,6-dipropyl-3-ethyl-2,6-dimethyi-4-oxo-piperidine, which are intermediates for the corresponding 1-oxo compounds.. Another method for the preparation of 2,2-dimethyl-6,6-dialkyl-4-oxopiperidine is described by F. AsinG6r, M. Thiel, H. Baltz, Monatshefte fur Chemie 88. 464 (1957) or by J. Bobbittt et al. in J. Org. Chem. 58, 4837 (1993). The oxidation of the piperidine compound to 1-oxo-piperidine derivatives is well known in the art and for example described by L.B. Volodarsky, V. A. Reznikov, V.I. Ovcharenko in Synthetic Chemistry of Stable Nitroxides, CRC Press, Boca Raton 1994. The nitroxides are then transformed into the NOR compounds of formula (I) or formulae (A) to (S) respectively, according to standard methods. Examples for suitable reactions are described in T.J. Connolly, M.V. Baldovi, N. Mohtat, J.C. Scaiano,: Tet. Lett. 3Z, 4919 (1996), I. Li, B.A. Howell et al.: Poiym. Prepr. 36, 469 (1996), K. Matyjaszewski.: Macromol. Symp. Ill, 47-61 (1996), P. Stipa, L Greci, P. CarlonI, E. Damiani.: Poiym. Deg. Stab. 55, 323 (1997), Said Oulad Hammouch, J. M. Catala.: Macromol. Rapid Commun. 17,149-154 (1996), Walchuk et al.: Polymer Preprints 39, 296 (1998) or Tan Ren, You-Cheng Liu, Qing-Xiang Guo.: Bull. Chem. Soc. Jpn. 69, 2935 (1996). The compounds containing a structural element of formula (I) are useful compounds for the preparation of oligomers, cooligomers, polymers or copolymers. Hence a further subject of the invention is there use as initiators for the polymerization of ethylenically unsaturated monomers. The following examples illustrate the invention. A) Preparation of Compounds 2,6-diethyl-2,3,6-trlmethyl-4-oxopiperidine and 2,6-dipropyl-3-ethyl-2,6-climethyl-4-oxo-piperidine are prepared according to example 1 and 2 of DE 26 21 841. Example 1: 2,6-diethyl-2,3,6-trlmethyl-4-hydroxyplperidine To a solution of 118.2g (0.6mol) 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine in 1000ml ethanol 18.2g (0.4 mol) sodium borohydride are added in portions and the temperature is kept below 30 °C. Subsequently the solution is stirred for 2 hours at 50°C. Ethanol is distilled off, 500 ml water are added to the residue which is subsequently extracted several times with CH2C12. The extract is dried over Na2S04 and the solution is filtered. After removing the solvent 116g (97%) 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidin are obtained as yellowish liquid. Elemental analysis calculated for C12H25NO: C 72,31%; H 12.64%; N 7.03%. Found: C 71.44%; H 12.71%; N 6.87%. Example 2: 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1 -oxyl To a solution of 25.7g (0.13 mol) 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine of example 1 In 120 ml tetrahydrofurane a solution of a solution of 54.5g (0.22 mol) m-chlor-perbenzoic acid (70%) in 230 ml tetrahydrofurane is droppwise added under stirring within 2 hours at 0°C. The red to brown solution is stirred over night at room temperature and 500 ml hexane, are added. The solution is neutralized by shaking several times with 1 N NaHCOa and finally with water. The solvent is evaporated and 27.0g (97%) 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl are obtained as red liquid. Elemental analysis calculated for C12H24NO2: C 67.25%; H 11.29%; N 6.54%. Found: C 67.10%; H 11.42%; N 6.68%. Example 3: 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine is prepared in analogy to example 2 by oxidizing 16g (0.08 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxopiperidine with m-chlor-perbenzoic acid. lOg 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl are obtained as red liquid. Elemental analysis calculated for C12H22NO2: C 67.89%; H 10.44%; N 6.60%. Found: C 68.00%; H 10.42%; N 6.61%. Example 4: 2,6-diethyl-2,3,6-trimethyl-4-propyloxypiperldine-1l-oxyl In a 200 ml three neck bottle 25.6g (0.12 mol) 2,6-diethyl-2,3,6-trimethyl-4-hydroxy-plperidine-1-oxyl, 16g (0.4 mol) sodium hydroxide, 3.86g (0.012 mol) tetrabutyl-ammonium-bromide, 16g water and 30ml toluene are added. The clear emulsion is heated up to 60°C and within 1 h 22.1 g (0.18 mol) propylbromide are dropwise added under stirring. The temperature is maintained for 12 h under stirring. The reaction mixture is cooled to room temperature, the water phase is separated and the organic phase is washed neutral with water and dried over Na2S04. The organic solvent is evaporated and the residue is distilled over a short column. 21g (68%) 2,6-diethyl-2,3,6-trimethyl-4-propyloxy-piperidine-1-oxyl are obtained as red liquid. Elemental analysis calculated for C15H30NO2: C 70,27%; H 11.79%; N 5.46%. Found: C 70,26%; H 11.90%; N 5.34%. Example 5: 2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidtne-1-oxyl The title compound is prepared in analogy to example 2. 5g (0.021 mol) 2,6-Dipropyl-2-ethyl-2,6-dimethyl-4-oxopiperidine are oxidized with m-chlor-perbenzoic acid. 5.5g 2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine-1-oxyl are obtained as red liquid. Elemental analysis calculated for C15H30NO2: C 70,27%; H 11.79%; N 5.46%. Found: C 72.31%; H 11.02%; N 5.07%. Bsp. 6: 1-Benzyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine (No. 101) In a reactor suitable for conducting photo reactions 150 ml toluene, 4.4g (0.02 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine-1-oxyl and 12.7g (0.087 mol) t-butylperoxide are added. The red solution is purG6d with nitroG6n and subsequently irradiated with a mercury immersion lamp under nitroG6n at 20-25°C. After 8 h the solution is colorless. The reaction mixture is concentrated and the residue is subjected to column chromatography (silicaG6l, hexane-ethylacetate (9:1)). 4.8 g (77%) 1-benzyloxy- 2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine are isolated as yellowish liquid. Elemental analysis calculated for C19H29NO2: C 75,20%; H 9.63%; N 4.61%. Found: C 75.53%; H 9.60%; N 4.59%. Example 7:1-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine (No. 102) The title compound is prepared in analogy to example 6. 8.5g (0.04 mol) 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl are reacted with t-butylperoxide in ethylbenzene. 10.5g (82 %) 1-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine are obtained as yellowish liquid. Elemental analysis calculated for C20H33NO2: C 75.43%; H 10.30%; N 4.35%. Found: C 75.54%; H 10.36%; N 4.40%. Example 8:1-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-propyloxypiperidine (No. 103) The title compound is prepared In analogy to example 6. 5.63g (0.022 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxypropylpiperidine-1-oxyl are reacted with t-butylperoxide in ethylbenzene. 6.1 g (77 %) 1-(1-phenylethoxy)-2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine are obtained as yellowish liquid. Example 9: 1 -t-butyloxy-2,6-diethyi-2,3,6-trimethyl-4-oxoplperidine (No. 104) The title compound is prepared in analogy to example 6. 4.77g (0.022 mol) 2,6-diethyl-2,3,6-trimethyl-4-oxypropyl-piperidine-1-oxy and 2.13g (0.015 mol) 2,2"-azobis(2-methyl-propane) are reacted in ethylbenzene. 1.15g 1-t-butyloxy-2,6-diethyl-2,3,6-trimethyl-4-oxypiperidine are obtained as yellowish liquid. Elemental analysis calculated for C16H31NO2: C 71.33%; H 11.60%; N 5,20%. Found: C 71,28%; H 11.67%; N 5.45%. Example 10: 1 -(1 -phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine (No. 105) The title compound is prepared in analogy to example 6. 5.0g (0.021 mol) 2,6-Dipropyl-2-ethyl-2,6-dimethyl-4-oxopiperidine-1-oxyl and t-butylperoxide are reacted in ethylbenzene. 3.4g (49 %) 1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine are obtained as yellowish liquid. Elemental analysis calculated for C23H37NO2: C 76.83%; H 10.37%; N 3.90%. Found: C 77.51%; H 10.49%; N 3.10%. Example 11: 1 -(1 -phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-hydroxy-piperidine Nr.106) The title compound is prepared in analogy to example 1. 3.1g (0.009 mol) 1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine is reduced withsodium-borohydride in ethanol. 2.9 g (93 %) 1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-hydroxypiperidine are obtained as yellowish liquid. Elemental analysis calculated for C23H39NO2 76.40%; H 10.87%; N 3.87%. Found: C 75.89%; H 11.14%; N 3.18%. Example 12: 2,2,6-trimethyl-6-ethyl-piperidine 33.8 g (0.2 mol) 2,2,6-trimethyl-6-ethyl-4-oxopiperidine, 14 g (0.28 mol) hydrazinhydrate and 13 g KOH in 80 ml diethylenglykol are stirred for 4 h at 160 °C. Subsequently an additional amount of 30 g KOH dissolved in 30 ml water are added. 30 ml are distilled off. To the residue two times 40 ml of water are added and removed by distillation. The combined distillates are saturated with solid K2CO3 and extracted with methyl-tert.-butylether. From the extracts 6 g (19%) 2,2,6-trimethyl-6-ethyl-piperidin are isolated by fractionated distillation. A colorless liquid is obtained with a b. p. of 78 - 88° C /15 mbar. ^H-NMR (CDCI3), 6 ppm: 1.8-1,2 m (4XCH2), 1.14 s (CH3), 1.1 s (CH3), 1.05 s (CH3), 0.86 t (CH3). Example 13: 2,2,6-Trimethyl-6-ethyl-piperidine-1-oxyl To a solution of 5.7 g (0.037 mol) 2,2,6-trimethyl-6-ethyl-piperidine in 20 ml methanol, 0.07g sodium wolframate and 10 ml of 30% hydroG6n peroxide are added. The mixture is stirred for 23 h at room temperature, diluted with a saturated NaCI solution and extracted with methyl-tert.-butylether. The combined extracts are dried over MgS04 and concentrated under vacuum. The residue is subjected to column chromatography (silica G6l, hexane-ethylacetate 9:1). 4.6 g (73%) pure 2,2,6-trimethyl-6-ethyl-1-oxyl are isolated as red oil. Elemental analysis calculated for C10H20NO: C 70.54%; H 11.84%; N 8.23%. Found: C 70.18%; H 12.02%; N 8.20%. Example 14:1-(Dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-piperidine (No 107) A solution of 2.8 g (0.016 mol) 2,2,6-trlmethyl-6-ethyl-plperidine-1-oxyl and 2.05 g (0.012 mol) azolsobutyronitril (AIBN) in 7 ml benzene are refluxed under argon atmosphere for 4 hours. Subsequently additional 1.5 g (0.009 mol) AIBN are added and the mixture is heated for one hour under argon. The colorless solution is concentrated under vacuum and subjected to column chromatography (silica G6l, hexane- ethylacetate 19:1). 1.63 g (42%) 1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-piperidine are isolated as colorless oil which slowly crystallizes to a solid with m. p. of 41 - 52 °C. Elemental analysis calculated for C14H26N2O: C 70.54%; H 10.99%; N 11.75%. Found: C 70.49%; H 10.71%; N 11.60%. Example 15: 2,2,6-Trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl To a solution of 27.2g (0.16mol) 2,2,6-trimethyl-6-ethyl-4-oxopiperidine in 100 ml methanol 3 g (0.08 mol) sodium borohydride are added in portions. The temperature is kept below 30 °C. After stirring over night 55 ml (0.64 mol) of 35% hydroG6n peroxide, 0.5 g sodium tungstate, 40 ml of 20% sodium carbonate and additional 60 ml methanol are added. After stirring for another 20 h at room temperature the reaction mixture is filtered, diluted with 100 ml saturated NaCI solution and subsequently extracted 3-times with hexane-methyl-tert.-butylether (1:1). The combined extracts are dried over MgS04 and concentrated under vacuum. The residue is subjected to column chromatography (silica G6l, hexane-ethylacetate 1:1). 12.5 g (42%) pure 2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl are isolated as red oil Elemental analysis calculated for C10NO2 C 64.48%; H 10.82%; N 7.52%. Found: C 63.73%; H 10.87%; N 7.24%. Example 16:1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine (No. 108) A solution of 2.0 g (0.0107 mol) 2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine-1-oxyl and 2.65 g (0.016 mol) azolsobutyronitril (AIBN) in 8 ml benzene is refluxed under argon for 30 minutes. The colorless solution is concentrated under vacuum and subjected to column chromatography (silica G6l, hexane- ethylacetate 2:1). The combined fractions are recrystallized from hexane. 2.0 g (73%) 1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine with a m. p. of 48 - 60 ° C are Isolated. Elemental analysis calculated for C14H26N2O2: C 66.11%; H 10.30%; N 11.01%. Found: C 65.77%; H 10.49%; N 11.04%. Example 17:1-(1-phenylethoxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidlne (No 109) 3.1g (0.0166 mol) 2,2,6-trimethyl-6-ethyl-4-hydroxyplperidine-1-oxyl, 2.2 g (0.0153 mol) Copper (I) bromide and 4.1 g (0.0153 mol) 4,4"-di-.tert.-butyl-[2,2"]bipyridinyl are added to 20 ml benzene. The solution Is purG6d with argon and evacuated for several times to remove the oxyG6n from the solution. With a syrinG6 2.79 g (0.0151 mol) 1-phenylethylbromide are added. The mixture is stirred for 21 h at room temperature. The green suspension is filtered over Cellit and the filtrate is removed from benzene under vacuum. The residue is subjected to column chromatography (silica G6l, hexane- ethylacetate 4:1). 2.18 g ( 45%) 1-(1-phenylethoxy)-2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine are obtained as colorless oil. Recrystallization from hexane results in crystals of a m. p. of 58 - 69 ° C. ^H-NMR (CDCI3), 5 ppm: 7.3 m 5 H (ArH), 4.75 m 1H (0CH(CH3)Ph), 3.88 m 1H (CHOH), 2.1 - 0.5 m 21H (4XCH3, 1x C2H5, CH2COCH2). Example 18: 2,2,6-Trlmethyl-6-lsopropyl-4-oxoplperidine The title compound is prepared in analogy to F. AsinG6r, M. Thiel, H. Baltz.: Monatshefte fur Chemie 88, 464 (1957) from mesityloxide, methylisopropylketone and ammonia. A colorless liquid is obtained. ^H-NMR (CDCI3), 5 ppm: 2.25 m 4H (CH2COCH2), 1.64 m 1H (CH(CH3)2), 1,24 s (CH3), 1.21 s (CH3), 1.07 s (CH3), 0.91 dd 6H (CH(CH3)2). Example 19: 2,2,6-trlmethyl-6-isopropyl-4-oxopiperldine-1-oxy1 2.75 g (0.015 mol) 2,2,6-trimethyl-6-isopropyl-4-oxopiperidine, 0.08 g sodium wolframate, 0.2 g sodium carbonate, 10 ml of 30% hydroG6n peroxide and 10 ml methanol are stirred for 22 h at room temperature. 20 ml saturated NaCI solution are added and the mixture is extracted 3-times with hexane-methyl-tert.-butylether (1:1). The combined extracts are dried over MgS04 and concentrated under vacuum. The residue is subjected to column chromatography (silica G6l, hexane- ethylacetate 4:1). 1.8 g (60%) pure 2,2,6-trimethyl-6-isopropyl-4-oxopiperidine are isolated as red oil. Recrystallization from pentane results in a solid of a m. p. of 47 - 53 ° C. Elemental analysis calculated for C11H20NO2: C 66.63%; H 10.17%; N 7.06%. Found: C 66.42%; H 10.19%; N 7.10%. Example 20:1-(dimethylcyanomethyl)-2,2,6-trimethyl-6-isopropyl-4-oxopiperidine (No 111) A solution of 1.0 g (0.005 mol) 2,2,6-trimethyl-6-isopropyl-4-oxopiperidine-1-oxyl and 1.6 g (0.01 mol) azoisobutyronitril (AIBN) In 5 ml benzene are refluxed under argon for 30 minutes. The colorless solution is concentrated under vacuum and subjected to column chromatography (silica G6l, hexane- ethylacetate 9:1). The combined fractions are recrystallized from hexane. 0.55 g (41%) 1-(dimethylcyanomethyloxy)-2,2,6-trimethyl-6-isopropyl-4-oxopiperidine with a m. p. of 32-44 °C are obtained. ^H-NMR (CDCI3), 6 ppm: 2.5 m 4H (CH2COCH2), 2.15 m 1H (CH(CH3)2), 1.69 s 6H ((CH3)2CCN), 1.37 s (CH3), 1.33 s (CH3), 1.26 s (CH3), 0.91 dd 6H (CH(CH3)2). Example 21:2,2-dlmethyi-6,6-dlethyl-4-hydroxypiperidine I To a solution of 15.8 g (0.086mol) 2,2-dimethyl-6,6-diethyl-4-oxopiperidine in 50 ml methanol 2.2 g (0.06 M) sodium borohydride are added in portions. The temperature is kept below 30 °C. After stirring over night methanol is removed under vacuum and the residue is diluted with 20 ml 2N-NaOH. The solution is extracted with ethylacetate. The combined extracts are washed with saturated NaCI solution, dried over MgS04 and dried under vacuum at 60°C / 50 mbar until a constant weight is achieved. 15.8 g (99%) 2,2-dimethyl-6,6-diethyl-4- hydroxypiperidine are obtained as yellowish oil. Example 22: 2,2-dimethyi-6,6-dlethyl-4-hydroxyplperldine-1-oxyl 15.85 g (0.085 mol) 2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine, 0.25 g sodium wolframate, 1 g sodium carbonate, 26 ml of 35% hydroG6n peroxide and 45 ml methanol are stirred for 28 h at room temperature. 100 ml saturated NaCI solution are added and the mixture is extracted 3-times with hexane-methyl-tert.-butylether (1:1). The combined extracts are dried over MgS04 and concentrated under vacuum. The residue is subjected to column chromatography (silica G6l, hexane- ethylacetate 2:1). 8.55 g (50%) pure 2,2-Dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl are isolated as red oil. Example 23:1-(1-phenylethoxy)-2,2-dimethyl-6,6-diethyl-4-hydroxyplperidine (No 110) 2.0g (0.01 mol) 2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl, 1.43 g (0.01 mol) Copper (I) bromide and 1.56 g (0.01 mol) 4,4"-di-.tert.-butyl-[2,2"]bipyridinyl are added to 20 ml benzene. The solution is purG6d with argon and evacuated for several times to remove the oxyG6n from the solution. With a syrinG6 1.85 g (0.01 mol) 1-phenylethylbromid are added. The mixture is stirred for 16 h at room temperature. Additional 0.3 g (0.002 mol Copper (I) are added under argon and the solution is stirred for another 23 h. The green suspension is filtered over Celllt and the filtrate is removed from benzene under vacuum. The residue is subjected to column chromatography (silica G6l, hexane- ethylacetate 3:1). After recrystallization from hexane 0.8 g 1-(1-phenylethoxy)-2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine with a m. p. of 84 - 86 °C are obtained. Elemental analysis calculated for C19H31NO2: C 74.71%; H 10.23%; N 4.59%. Found: C 74.77%; H 10.39%; N 4.55%. Example 24:1-(1-phenylethoxy)-2,3,6-trimethyl-2,6-diethyl-4-oxopiperidine (Nr 112) The title compound is prepared in analogy to example 6. 4.7g (0.022 mol) 2,6-diethyl-2,3,6-trimethyi-4-oxypiperidine-1 -oxyl are reacted with t-butylperoxide in ethyibenzene. 5.0g (71 %) 1-(1-phenylethoxy)-2,6-dipropyl-2-ethyl-2,6-dimethyl-4-oxypiperidine are obtained as yellowish liquid. Elemental analysis calculated for C20H31NO2: C 75.67%; H 9.84%; N 4.41%. Found: C 75.60%; H 9.77%; N 4.34%. Example 25:1-(1-phenylethoxy)-2,2-dlmethyi-6,6-diethyl-4-benzoyloxypiperidine (No 113) A) 2,2-Dimethyl-6,6-diethyl-4-benzoyloxypiperidine-1 -oxyl To a stirred solution of 6.05g (0.03 mol) of 2,2-dimethyl-6,6-diethyi-4-hydroxypiperidine-1-oxyl in 20 ml of pyridine are slowly and under cooling with ice added 3.8 ml (0.032 mol) of benzoylchloride. Afterwards, the mixture is stirred for 3.5 h at room temperature, then diluted with 200 ml of water and extracted twice with 50 ml of hexane. The combined extracts are washed with water, dried over MgS04 and evaporated in vacuo to G1ve 9.1 g of 2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine-1-oxyl as a thick, red oil. Elemental analysis calculated for C18H26NO3: C 71.02%; H 8.61%; N 4.60%. Found: C 70.96%; H 8.76%; N 4.53%. B) 3.04 g (0.01 mol) of 2,2-dimethyl-6,6-dlethyl-4-benzoyloxypiperidine-1-oxyl and 7.37 ml of t-butylperoxide in 200 ml of ethyibenzene are photolyzed as described in example 6 to afford 5.5 g of 1 -(1 -phenylethoxy)-2,2-dimethyl-6,6-diethyl-4-benzoyloxypiperidine as a thick colorless oil. "H-NMR (CDCI3), d ppm: 0.5 - 2.0 m (23H), 4.74 m (1H), 5.2 m (1H), 7.2-7.6 m (8 H), 8.00-8.03 d(2 H). Example 26: 2,6-diethyl-2,3,6-trimethyl-4-lauroyloxyplperldine-1 -oxyl To a stirred solution of 21,4g (0.1 mol) of 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl in 15 ml triethylamine and 70 ml toluene are slowly and under cooling with ice added 19.9g (0.091 mol) of lauroyl chloride. Afterwards, the mixture is stirred for 6 hrs at room temperature, then diluted with 200 ml of water and extracted twice with 100 ml of toluene . The combined extracts are washed with water, dried over MgSO4 and evaporated in vacuo and the residue is subjected to column chromatography (silicaG6l, hexane-ethylacetate (5:1)). 25,2 g (64%) 2,6-diethyl-2,3,6-trimethyl-4-lauroyloxypiperidlne-1-oxyl are isolated as a red oil. Elemental analysis calculated for C24H46NO3: C 72,67%; H 11,69%; N 3,53%. Found: C 72,39%; H 11,60%; N 3,30%. Example 27: 2,6-diethyl-2,3,6-trimethyl-4-stearoyloxypiperldine-1 -oxyl To a stirred solution of 5g (0.023 mol) of 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1-oxyl in 5 ml triethylamine and 40 ml toluene are slowly and under cooling with ice added 7,1 g (0.021 mol) of stearyl chloride. Afterwards, the mixture is stirred for 6 hrs at room temperature, then diluted with 100 ml of water and extracted twice with 50 ml of toluene . The combined extracts are washed with water, dried over MgS04 and evaporated in vacuo and the residue is subjected to column chromatography (silicaG6l, hexane-ethylacetate (5:1)). 5,8 g (52%) 2,6-diethyl-2,3,6-trimethyl-4-stearoyloxypiperidine-1-oxyl are isolated as a red oil. Elemental analysis calculated for C30H58NO3: C 74.94 %; H 12.16 %; N 2.91 %. Found: C 74.96 %; H 12.00 %; N 2.69 %. Example 28: 2,2-dlmethyl-6,6-dlethyi-4-lauroyloxypiperldine-1-oxyl To a stirred solution of 2,0g (0.01 mol) of 2,2-dimethyl-6,6-diaethyl-4-hydroxypiperidine-1-oxyl in 2 ml triethylamine and 25 ml toluene are slowly and under cooling with ice added 2,0g (0.0091 mol) of lauroyl chloride. Aftenwards, the mixture is stirred for 6 hrs at room temperature, then diluted with 50 ml of water and extracted twice with 25 ml of toluene . The combined extracts are washed with water, dried over MgS04 and evaporated in vacuo and the residue is subjected to column chromatography (silicaG6l, hexane-ethylacetate (5:1)). 1,8 g (48%) 2,2-dimethyl-6,6-diethyl-4-lauroyloxypiperidine-1-oxyl are isolated as a red oil. Elemental analysis calculated for C23H44NO3: C 72,20%; H 11,60%; N 3,66%. Found: C 72,01%; H 11,61%; N 3,48%. Example 29: 2,2-dimethyl-6,6-diethyl-4-stearoyloxypiperidine-1-oxyl To a stirred solution of 5,0g (0.025 mol) of 2,2-dimethyl-6,6-diethyl-4-hydroxypipericline-1-oxyl in 5 ml triethylamine and 40 ml toluene are slowly and under cooling with ice added 7,9g (0.023 mol) of stearoyl chloride. Afterwards, the mixture is stirred for 6 hrs at room temperature, then diluted with 100 ml of water and extracted twice with 50 ml of toluene . The combined extracts are washed with water, dried over MgSO4 and evaporated in vacuo and the residue is subjected to column chromatography (silicaG6l, hexane-ethylacetate (5:1)). 6,15 g (52%) 2,2-dimethyl-6,6-diaethyl-4-stearoyloxypiperidine-1-oxyl are isolated as a red oil. Elemental analysis calculated for C29H56NO3: C 74.62 %; H 12.09 %; N 3.00 %. Found: C 74.47 %; H 12.03 %; N 2.99 %. Example 30: 2,6-diethyl-2,3,6-trimethyl-4-propoxypiperidine-1 -oxyl To a stirred solution of 128g (0.6 mol) of 2,6-diethyl-2,3,6-trimethyl-4-hydroxypiperidine-1 -oxyl, 80g NaOH, 80g water, 19,3g tetrabutylammonium bromide and 240 ml toluene are slowly added at 50 °C 111 g (0.9 mol) of propylbromide. Afterwards, the mixture is stirred for 10 hrs at 50 °C, then diluted with 200 ml of water and the organic phase is separated . The organic phase is washed with water, dried over MgSO4 and evaporated in vacuo. The raw product is purified by destination. 81g (54%) 2,6-diethyl-2,3,6-trimethyl-4-propoxypiperidine-1-oxyi are isolated as a red oil. Elemental analysis calculated for C15H30NO2: C 70,27%; H 11,79%; N 5,46%. Found: C 70,26%; H 11,88%; N 5,40%. B) Polymerizations using compounds of Table 1 or their N-0. precursors as initiators G6neral remarks: Solvents and monomers are distilled over a Vigreux column under argon atmosphere or under vacuum, shortly before being used. To remove oxyG6n all polymerization reaction mixtures are flushed before polymerization with argon and evacuated under vaccum applying a freeze-thaw cycle. The reaction mixtures are then polymerized under argon atmosphere. At the start of the polymerization reaction, all starting materials are homoG6neously dissolved. Conversion is determined by removing unreacted monomers from the polymer at 80°C and 0.002 torr for 30j7iinutes , weighing the remaining polymer and subtract the weight of the initiator. Characterization of the polymers is carried out by MALDI-MS (Matrix Assisted Laser Desorption Ionization Mass Spectrometry) and/or GPC (G6l Permeation Chromatography). MALDI-MS: Measurements are performed on a linear TOP (Time Of Flight) MALDI-MS LDI-1700 Linear Scientific Inc., Reno, USA. The matrix is 2,5-dihydroxybenzoic acid and the laser wavelength is 337 nm. GPC: Is performed using RHEOS 4000 of FLUX INSTRUMENTS. Tetrahydrofurane (THF) is used as a solvent and is pumped at 1 ml/min. Two chromatography columns are put in series: type PIG6l 5μm mixed-C of POLYMER INSTRUMENTS, Shropshire, UK. Measurements are performed at 40 °C. The columns are calibrated with low polydispersity polystyrenes having Mn from 200 to 2 000 000 Dalton. Detection is carried out using a Rl-Detector ERC-7515A of ERCATECH AG at 30 °C. B) Polvmerizations with Acrvlates B1-B10 Homopolymers bxampie m. Koiymerizaiion or n-Dutylacrvlate using compound 101 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 710 mg ( 2.34 mmol) of compound 101 and 20 g (156 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 5 h. The reaction mixture is then cooled to 80 °C. The remaining monomer is removed by evaporation under high vacuum. 19.3 g (93%) of the initial monomer have reacted. A clear colorless viscous fluid is obtained. GPC: Mn = 12000 , Mw = 21300 , Polydispersity (PD) = 1.77 Example B2. Polymerization of n-butvlacrvlate using compound 102 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 743 mg ( 2.34 mmol) of compound 102 and 20 g (156 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 5 h. The reaction mixture is then cooled to 80 °C. The remaining monomer is removed by evaporation under high vacuum. 16.8 g (80%) of the initial monomer have reacted. A clear colorless viscous fluid is obtained. GPC: Mn = 7500 , Mw = 8700 , Polydispersity (PD) =1.16 Example B3. Polymerization of n-butvlacrvlate using compound 103 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 4.51 g (12.5 mmol) of compound 103 and 16 g (125 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 5 h. The reaction mixture is then cooled to 80 °C. The remaining monomer is removed by evaporation under high vacuum. 14.9 g (65%) of the initial monomer have reacted. A clear oranG6 viscous fluid is obtained. The raw prodct is is subjected to column chromatography (silica G6l, hexane- ethylacetate 1:4) and 10.4 g of a colorless viscous liquid is obtained. GPC: Mn = 1550 , Mw = 1900 , Polydispersity (PD) = 1.22 Example B4. Polymerization of n-butvlacrvlate using compound 104 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 473 mg (1.76 mmol) Nr 104 and 15 g (117 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 5 h. The reaction mixture is then cooled to 80 °C. The remaining monomer is removed by evaporation under high vacuum. 1.65 g (11%) of the initial monomer have reacted. A clear slight oranG6 viscous fluid is obtained. Example B5. Polymerization of n-butvlacrvlate using compound 106 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 844 mg (2.34 mmol) of compound 106 and 20 g (156 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 2 h. The reaction mixture is then cooled to 80 °C. The remaining monomer is removed by evaporation under high vacuum. 16.8 g (80%) of the initial monomer have reacted. A clear colorless viscous fluid is obtained. After 2 h 15.2 g (76%) of the initial monomer have reacted. A clear colorless viscous fluid is obtained. GPC : Mn = 6550 , Mw = 8100, Polydispersity (PD) = 1,24 Example B6. Polymerization of n-butvlacrvlate using compound 110 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 357 mg (1.2 mmol) of compound 110 and 10 g (78 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 5 h. The reaction mixture is then cooled to 80 °C. The remaining monomer is removed by evaporation under high vacuum. 7.6 g (76%) of the initial monomer have reacted. A clear slightly oranG6 viscous fluid is obtained. GPC: Mn = 6100, Mw = 7500 , Polydispersitat (PD) =1.2 Example B7. Polymerization of n-butylacrylate using compound 112 In a 50 ml three neck flask, equipped with thermometer, cooler and magnetic stirrer, 743 mg (2.34 mmol) of compound 112 and 20 g (156 mmol) of n-butylacrylate are mixed and degased. The clear solution obtained is heated under argon to 145 °C and polymerization is carried out during 5 h. The reaction mixture is then cooled to 60 °C. The remaining monomer is removed by evaporation under high vacuum. 16 g (80%) of the initial monomer have reacted. A clear slightly oranG6 viscous fluid is obtained. GPC: Mn = 7500 , Mw = 8700 , Polydispersitat (PD) =1.2 MALDI-TOF: Mn = 6400 , Mw = 7700 , Polydispersitat (PD) = 1.2 Example 88. Polymerization of dimethvlaminoethviacrvlate using compound 102 A 50ml round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 0.268 g (0.8 mmol) of compound 102 and 8 g (56 mmol) of dimethylaminoethylacrylate and degassed. The clear yellow solution is then heated to 145°C under argon. The mixture is stirred for 1 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 5.6 g (70%) of a brown viscous polymer are obtained. GPC : Mn = 2300, IVIw = 3700, Polydispersity = 1.6 Example B9. Polymerization of dimethvlaminoethvlacrvlate using compound 110 A 50ml round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 0.256 g (0.8 mmol) of compound 110 and 8 g (56 mmol) of dimethylaminoethylacrylate and degassed. The clear yellow solution is then heated to 145°C under argon. The mixture is stirred for 1 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 5.7 g (72%) of a brown viscous polymer are obtained. GPC : Mn = 2100, Mw = 3300, Polydispersity = 1.6 Example BIO. Polymerization of t-butvlacrvlate using compound 110 A round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 0.178 g (0.6 mmol) of compound 110 and 5 g (39 mmol) of t-butylacrylate and degassed. The clear solution is then heated to 145°C under argon. The mixture is stirred for 3 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 1 g (20%) of a brown viscous polymer are obtained. GPC : Mn = 1800, Mw = 2900, Polydispersity = 1.6 B11-B15 Blockcopoiymers Example B11. Copolymerization of polv-n-butvlacrvlate made with compound 102 with n-butyiacrvlate A round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 12 g (93 mmol) n-butylacrylate and 12.5 g of poly-n-butylacrylate (made with compound 102, Mn=7500, PD=1.2) and degassed. The solution is then heated to 145°C under argon. The mixture is stirred for 5 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 20% of the additional monomer is reacted and an oranG6 viscous liquid is obtained. GPC : Mn = 8500, Mw = 11400, Polydispersity = 1.4 Example B12. Copolvmerization of polv-n-butvlacrvlate made with compound 102 with dimethvlaminoethylmethacrvlate equipped with thermometer, condenser and magnetic stirrer is charG6d with 14.5 g (93 mmol) dimethylaminoethylmethacryiate and 12.5 g of poly-n-butyiacrylate (made with compound 102, Mn=7500, PD=1.2) and degassed. The solution is then heated to 145°C under argon. The mixture is stirred for 5 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 10% of the additional monomer is reacted and an oranG6 viscous liquid is obtained. GPC : Mn = 8200, Mw = 13200, Polydisperslty =1.6 Example B13. Cooolvmerization of polv-n-butvlacrvlate made with compound 110 with n-butvlacrvlate A round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 11 g (86 mmol) n-butylacrylate and 11.5 g of poly-n-butylacrylate (made with compound 110, Mn=5600, PD=1.3) and degassed. The solution is then heated to 145°C under argon. The mixture is stirred for 5 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 10% of the additional monomer is reacted and an oranG6 viscous liquid is obtained. GPC : Mn = 6500, Mw = 8500, Polydispersity = 1.3 Example B14. Copolymerization of polv-n-butvlacrvlate made with compound 110 with dimethvlaminoethvlmethacrvlate (50 / 50) A round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 5 g (37 mmol) dimethylaminoethylmethacryiate and 5 g of poly-n-butylacrylate (made with compound 110, Mn=5600, PD=1.3) and degassed. The solution is then heated to 145°C under argon. The mixture is stirred for 3 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 20% of the additional monomer is reacted and an oranG6 viscous liquid is obtained. GPC : Mn = 5500, Mw = 7400, Polydispersity = 1.3 Example B15. Copolvmerization of polv-n-butvlacrvlate made with compound 110 with dimethvlaminoethvlmethacrvlate (20 / 80) A round-bottom three necked flask, equipped with thermometer, condenser and magnetic stirrer is charG6d with 18 g (115 mmol) dimethylaminoethylmethacryiate and 4 g of poly-n-butylacrylate (made with compound 110, Mn=5600, PD=1.3) and degassed. The solution is then heated to 145°C under argon. The mixture is stirred for 3 hour at 145°C and then cooled to 60°C and the remaining monomer is evaporated under high vacuum. 30% of the additional monomer is reacted and an oranG6 viscous liquid is obtained. GPC : Mn = 10000, Mw = 17700, Polydispersity = 1.8 C) Polymerizations with Styrene Homopolymerization with NOR Example CI: Polymerization of styrene using compound 102 50 ml of styrene and 0.087mol/l of compound 102 are heated under argon for 6 hrs to 130 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. 33 g (66 %) of a colorless polymer are obtained. GPC:Mn = 8000, Mw = 9100, Polydispersity =1,14 Example C2: Polvmerization of styrene using compound 102 50 ml of styrene and 0,0087mol/l of compound 102 are heated under argon for 6 hrs to 130 "C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. 37,5 g (75 %) of a colorless polymer are obtained. GPC: Mn = 48400, Mw = 67200, Polydispersity = 1,39 Homopolymerization with nitroxide + benzoylperoxide (BPO) Example C3: Polvmerization of stvrene using nitroxide from Example A2 + (BPO) 50 ml of styrene, 0,0087 mol/l nitroxide (from Example 2) and 0,0069 mol/l BPO are heated under argon for 6 hrs to 120 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. 27,5 g (55 %) of a colorless polymer are obtained. GPC: Mn = 48100, Mw = 61500, Polydispersity = 1,28 Example C4: Polvmerization of stvrene using nitroxide from Example A2 + BPO 100 ml of styrene, 0,087 mol/l nitroxide (from Example 2) and 0,069 mol/l BPO are heated under argon for 6 hrs to 120 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. 35 g (35 %) of a colorless polymer are obtained. GPC: Mn = 6200, Mw = 7000, Polydispersity =1,13 Example C5: Polymerization of stvrene using nitroxide from Example A26 + BPO 50 ml of styrene, 0,087 mol/l nitroxide (from Example 26) and 0,069 mol/l BPO are heated under argon for 6 hrs to 130 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. 39 g (78 %) of a colorless polymer are obtained. GPC: Mn = 9000, Mw = 10600, Polydispersity = 1,18 Example C6: Polymerization of stvrene using nitroxide from Example A26 + BPO 50 ml of styrene, 0,0087 mol/l nitroxide (from Example 26) and 0,0069 mol/l BPO are heated under argon for 6 hrs to 130 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. 40 g (80 %) of a colorless polymer are obtained. GPC: Mn = 50600, Mw = 72000, Polydispersity = 1.43 Example C7: Copolvmerization Stvrene / Stvrene 5 ml of polystyrene from Example 4 and 5 g of styrene are heated under argon for 6 hrs to 130 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. A colorless polymer is obtained. GPC: Mn = 9500, Mw = 12000, Polydispersity = 1,27 Example C8: Copolymerization Stvrene / n-Butvlacrvlate 5 ml of polystyrene from Example C4 and 5 g of n-butylacrylate are heated under argon for 6 hrs to 130 °C. The reaction mixture is then cooled to 80 °C and the remaining monomer is removed by evaporation under high vacuum. A colorless polymer is obtained. GPC: Mn = 8200, Mw = 9700, Polydispersity =1,18 Claims We Claim :- 1. A process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of an initiator compound of formula A, B, or O under reaction conditions capable of effecting scission of the 0-C bond to form two free radicals, the radical -X being capable of initiating polymerization, wherein A, B and O are as defined below G1, G2, G3, G4 are independently alkyl of 1 to 4 carbon atoms with tlie proviso that at least one is not methyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together are pentamethylen; G5, Ge are independently hydrogen or C1-C4ail R if m is 1, is hydrogen, C1-C8alkyl which is uninterrupted or C2-Ci8alkyl interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,p-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; or R is a monovalent radical of a carbamic acid or phosphorous containing acid or a monovalent silyl radical; R, if m is 2, is C2-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms; or R is a divalent radical of a phosphorus-containing acid or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; R, if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; pis 1; Ri is C1-C12alkyl, C5-C7cycloalkyi or benzoyl; R2 is C1-C12alkyl, C5-C7cycloalkyI or a group of the formula -CO-Z wherein Z is hydrogen, methyl or phenyl and X is selected from the group consisting of (C5-C6cycloalkyi)2CCN, (d-dgalkyOsCCN, -CH2CH=CH2, (C1-C12)alkyl-CR20-C(O)-(G1-Ci2)alkyl, (C1-C12)alkyl-CR2o-C(0)-(C6-Cio)aryl, (C1-C12)alkyl-CR20-C(O)-(CrCi2)alkoxy, (d-Ci2)alkyl-CR20-C(O)-phenoxy, (C1-C12)alkyl-CR20-C(O)-N-di(C1-C12)alkyl, (C1-C12)alkyl-CR2o-CO-NH(C1-C12)alkyl, (C1-C12)alkyl-CR20-CO-NH2, -CH2CH=CH-CH3, -CH2-C(CH3)=CH2, -CH2- Rzo is hydrogen or C1-C12alkyl; the aryl groups are phenyl or naphthyl, unsubstituted or substituted with C1-C12alkyl, halogen, C1-C12alkoxy, C1-C12alkylcarbonyl, glycidyloxy, OH, -COOH or -COOC1-C12alkyl. 2. Aprocess according to claim 1, wherein Ge is hydrogen and G5 is hydrogen or C1-C4a!kyl. 3. A process according to claim 1, wherein G1 and G3 are methyl and G2 and G4 are ethyl or propyl. 4. A process according to claim 1, wherein G1 and G2 are methyl and G3 and G4 are ethyl or propyl. 5. A process according to claim 1 wherein m is 1, R is hydrogen, C1-C8alkyl which is uninterrupted or C2-C18alkyl which is interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,b-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; pis 1; Ri is C1-C12alkyl, Cs-CTcycloalkyI or benzoyl; R2 is C1-C8alkyl, C5-C7cycJoalkyl or a group of the formula of the formula -CO-Z wherein Z is hydrogen, methyl or phenyl. 6. A process according to claim 5, wherein R is hydrogen, C1-C8alkyl, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic, carboxylic acid having 2 to 18 carbon atoms; Ri is C1-C12alkyl, Cs-C/cycioalkyI or benzoyl; R2 is C1-C12alkyl, Cs-Crcycloalkyi or a group of the formula -CO-Z wherein Z is hydrogen, methyl or phenyl. 7. A process according to claim 1, wherein X is selected from the group consisting of -CH2-phenyl, CHgCH-phenyl, (CH3)2C-phenyl, (Cg-CecycloalkyOaCCN, (CH3)2CCN, -CH2CH=CH2, CH3CH-CH=CH2 (C1-C8alkyl)CR20-C(O)-phenyl, (C1-C8)alkyl-CR2o-C(0)-(Ci-C8)alkoxy, (C1-C8)alkyl-CR2o-C(0)-(C1-C8)alkyl, (C1-C8)alkyl-CR20-C(0)-N-di(C1-C8)alkyl, (d-C8)alkyl-CR20-C(O)-NH(C1-C8)alkyl,(C1-C8)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-C8)alkyl. 8. A process according to claim 1, wherein X is selected from the group consisting of -CH2-phenyl, CHgCH-phenyl, (CH3)2C-phenyi, (Cs-CgcycloalkyOgCCN, (CH3)2CCN, -CH2CH=CH2, CH3CH-CH=CH2 (C1-C4alkyl)CR20-C(O)-phenyl, (C1-C4)alkyl-CR2o-C(0)-(Ci- C4)alkoxy, (C1-C4)alkyl-CR2o-C(0)-(C1-C4)alkyl, (C1-C4)alkyl-CR2o-C(0)-N-di(C1-C4)alkyl, (Ci- C4)alkyl-CR20-C(O)-NH(C1-C4)alkyl,(C1-C4)alkyl-CR20-C(O)-NH2, wherein R20 is hydrogen or (C1-C4)alkyl. 9. A process according to claim 1, wherein the ethylenically unsaturated monomer or oligomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriies, (alkyi)acrylamides, vinyl halides or vinyiidene haiides. 10. A process according to claim 9 wherein the ethylenically unsaturated monomer is ethylene, propylene, n-butylene, i-butylene, isoprene, 1,3-butadiene, a-Cs-Ciaalkene, styrene, a-methyl styrene, p-methyl styrene or a compound of formula CH2=C(Ra)-(C=Z)-Rb, wherein Rg is hydrogen or C1-C4alkyl, Rb is NH2, OXMe""), glycidyl, unsubstituted Ci- Ci8alkoxy, C2-Ciooalkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted Ci-Ciaalkoxy, unsubstituted C1-C18alkylamino, di(C1-C8alkyl)amino, hydroxy-substituted Cr Ci8alkylamino or hydroxy-substituted di(C1-C8alkyl)amino, -0-CH2-CH2-N(CH3)2 or -O-CH2- CH2-N+H(CH3)2 An"; An" is a anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or the ammonium ion; Z is oxygen or sulfur. 11. A process according to claim 10, wherein Ra is hydrogen or methyl, Rb is NH2, gycidyl, unsubstituted or with hydroxy substituted C1-C4alkoxy, unsubstituted C1-C4alkylamino, di(Ci- ^1 C4alkyl)amino, hydroxy-substituted C1-C4alkylamino or hydroxy-substituted di(Ci- C4alkyl)amino;and Z is oxygen. 12. A process according to claim 1, wherein the ethylenically unsaturated monomer is styrene, methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylamlnoethylacrylate, glycidylacrylates, metliyl(metii)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(metli)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide or dimethylaminopropyl-methacrylamide. 13. A process according to claim 1, wherein the initiator compound is present in an amount of from 0.01 mol-% to 30 mol-% , based on the monomer or monomer mixture. 14. A process according to claim 1, wherein the scission of the 0-C bond is effected by ultrasonic treatment, heating or exposure to electromagnetic radiation, ranG1ng from y to microwaves. 15. A process according to claim 1, wherein the scission of the 0-C bond is effected by heating and takes place at a temperature of between 50°C and 160°C. 16. A process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block or random) by free radical polymerization of at least one ethylenically unsaturated mono-mer/oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of a compound of formula A", B" or O" and a radical initiator capable of initiating polymerization of ethylenically unsaturated monomers wherein A", B" and O" are as defined below wherein G1, G2, G3, G4 are independently alky! of 1 to 4 carbon atoms with the proviso that at least one is not methyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together are pentamethylen; G5, Ge are independently hydrogen or C1-C4alkyl; R if m is 1, is hydrogen, C1-C18alkyl which is uninterrupted or C2-C18alkyl interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an a,P-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; or R is a monovalent radical of a carbamic acid or phosphorous containing acid or a monovalent silyl radical; R, if m is 2, is C2-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms; or R is a divalent radical of a phosphorus-containing acid or a divalent silyl radical; R, if m is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; R, if m is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid; p is 1; Ri is C1-C12alkyl, C5-C7cycloalkyl or benzoyl; R2 is C1-C12alkyl, C5-C7cycloalkyl or a group of the formula -CO-Z wherein Z is hydrogen, methyl or phenyl.

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0275-mas-1999 abstract-duplicate.pdf

0275-mas-1999 abstract.pdf

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0275-mas-1999 claims.pdf

0275-mas-1999 correspondence-others.pdf

0275-mas-1999 correspondence-po.pdf

0275-mas-1999 description (complete)-duplicate.pdf

0275-mas-1999 description (complete).pdf

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0275-mas-1999 petition.pdf