Title of Invention	N-ALKOXY-4,4-DIOXY-POLYALKYL-PIPERIDINES AS RADICAL POLYMERIZATION INITIATORS
Abstract	The present invention relates to selected glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polaylkyl-piperidine compounds forming an open chain or cyclic ketal structure, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiator compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers and the use of glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiators for radical polymerization.

Title of Invention

N-ALKOXY-4,4-DIOXY-POLYALKYL-PIPERIDINES AS RADICAL POLYMERIZATION INITIATORS

Abstract

The present invention relates to selected glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polaylkyl-piperidine compounds forming an open chain or cyclic ketal structure, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiator compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers and the use of glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiators for radical polymerization.

Full Text	N-ALK0Xy-4,4-DI0XY-P0LyALICYL-PIPERIDINES AS RADICAL POLYMERIZATION INITIATORS The present invention relates to selected glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds forming an open chain or cyclic ketal structure, a polymerizabie composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiator compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers and the use of glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiators for radical polymerization. The compounds of the present invention provide polymeric resin products having low polydispersity and the polymerization process proceeds with good monomer to polymer conversion efficiency. In particular, this invention relates to stable free radical-mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, multiblock copolymers, graft copolymers and the like, at enhanced rates of polymerization and enhanced monomer to polymer conversions. US-A-4 581 429 to Solomon et al., issued April 8, 1986. discloses a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligo-meric homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R'R-N-0-X, where X is a free radical species capable of polymerizing unsaturated monomers. The reactions typically have low conversion rates. Specifically mentioned radical R'R-N-0« groups are derived from 1,1,3,3 tetraethylisoindoline, 1,1,3,3 tetrapropyiisoindoline. 2,2,6,6 tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine or di-t-butylamine. However, the suggested compounds do not fulfill all requirements. Particulariy the polymerization of acrylates does not proceed fast enough and/or the monomer to polymer conversion is not as high as desired. The radical initiators, polymerization processes and resin products of the present invention have an additional glycidyl or carbonyl group, which can be used for further reactions. The resulting resins are useful in many applications. The glycidyl or alkylcarbonyl group of the present initiators remains essentially unchanged during the radical polymerization reaction. Therefore the radical initiators of the present invention offer the possibility, after the radical polymerization is accomplished or stopped, to react the glycidyl group of the oligomers or polymers in a second step with nucleophiles such as alcohols, mercaptanes, amines, metal organic compounds or the like, thereby changing the properties of the oligomers or polymers. The glycidyl group of the initiators can also be reacted in a first step for example by anionic polymerization in the presence of for example dicyandiamide, butyl-Lithium or other strong bases leading to oligomeric/polymeric radical initiators. S. Kobatake et al, Macromolecules 1997, 30. 4238-4242 and in WO 97/36894 disclose the anionic polymerization of butadiene in the presence of compound (a) which contains a glycidyl group in a side chain. This compound acts as a terminating reagent for the anionic polymerization of butadiene. The resulting macromolecule can be further used as a macroinitiator for radical polymerization and for preparing block copolymers containing a poylbutadiene segment. Typical copolymers which can be produced are acrylnitriie/butadiene/styrene (ABS) copolymers. The present invention provides initiators for radical polymerization which contain the glycidyl or alkylcarbonyl group attached to the phenyl group. The initiators show a high reactivity, good rates of polymerization and good monomer to polymer conversions. The remaining glycidyl or carbonyl group is highly reactive towards nucleophiles and can readily be transformed into other chemical groups if desired. The compounds of the present invention are also useful as terminating agents in the anionic polymerization of for example butadiene as described in WO 97/36894. With the instant compounds termination of anionic polymerization of for example butadiene proceeds fast and complete. Glycidyl or carbonyl functional alkoxyamines containing a tetramethyl-piperidine group and their use as functionaiized radical initiators/regulators have already been described in WO 99/46261. The instant compounds differ from those disclosed in WO 99/46261 in that they have a ketal structure in 4 position of the piperidine moiety. Such compounds and their use as polymerization initiators/regulators have neither been disclosed as specific compounds nor generically in the prior art. It has now been found, that amongst those 2,2,6.6-tetraalkylpiperidines described in the prior art those are of particular value which are derivatives of 2,2,6.6 tetramethyl piperidine, 2,2 diethyl-6,6 dimethyl piperidine and of 2,6-diethyl-2,3,6-trimethyl piperidine which are substituted in the 4 position by two oxygen atoms forming an open chain or cyclic ketal structure. The ketal stnjcture in 4 position ensures high thermal stability which is important for storage, particulariy at elevated temperatures. The ketal structure is themially significantly more • stable compared to the corresponding 4-oxo compound. The compounds exhibit an unchanged initiating/regulating activity even after storage at elevated temperatures as for example used in conventional stability tests. Another problem associated with nitroxyl or nitroxyl ether mediated free radical polymerization is the formation of a significant color of the resulting polymer. The compounds of the present invention which have a ketal structure in 4-position impart less color to the polymer compared to other prior art compounds of similar structure. The steric hindrance introduced by the two diethyl groups instead of two methyl groups further leads to an optimized balance in temis of stability of the compounds, initiating activity and control of polymerization. The particular substitution pattern in 2 and 6 position of the piperidine ring allows high monomer to polymer conversions in short times and low polydispersities which are generally below 2. High monomer to polymer conversions are even achieved with acrylates, such as ethyl- or butyl-acrylate. The temperature necessary to achieve high conversion in short times may be for example as low as 120°C. The present invention provides compounds useful as initiators/regulators for controlled radical polymerization which in addition have a highly reactive functional group allowing polymer analogous reactions or anionic polymerization termination, which can be adjusted in their initiating/controlling efficiency by adjusting the steric hindrance at the nitrogen atom and which have an excellent storage stability and impart none or only little color to the final polymer. R13 is phenyl or C1-C18alkyl; m is 1, 2 or 3; n is 1 or 2; if n is 1 Y and Y' are independently C1-C12alkyl. C3-C12alkenyl, C3-C12alkinyl, Cs-CecycloalkyI, phenyl, naphthyl, Cy-Cgphenylalkyi; or Y and Y' together fomi one of the bivalent groups -C(R0(R2)-CH(R3)-, CH(Ri)-CH2- C(R2)(R3)-. -CH(R2)-CH2-C(R0(R3)-> -CH2-C(R0(R2)-CH(R3)-. o-phenylene, 1,2- cyciohexyliden, Z is Ci-Ci2alkylene; the R12 are independently of each other H or CH3. C1-C18alkyi can be linear or branched. Examples 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, heptadecyl or octadecyl. Alkenyl having from 3 to 12 carbon atoms is a branched or unbranched radical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl. Alkinyl having from 3 to 12 carbon atoms is a branched or unbranched radical, for example propinyl ( —CH2-C=ECH ). 2-butinyl, 3-butinyI, n-2-octinyl or n-2-dodecinyL Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy. isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy. Cr-Cgphenylaikyi is for example benzyl, a-methyibenzyl. a,a-dimethylbenzyl or 2-phenylethyl, benzyl is preferred. C1-C12alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. C5-C8cycloalkyI is for example cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl or cyclooctyl. Examples of a monocarboxylic acid having up to 18 carbon atoms are formic acid, acetic acid, propionic acid, the isomers of valeric acid, methyl ethyl acetic acid, trimethyl acetic acid, capronic acid, lauric acid or stearic acid. Examples for unsaturated aliphatic acids are acrylic acid, methacrylic acid, crotonic acid, linolic acid and oleic acid. Typical examples of cycloaliphatic carboxylic acids are cyclohexane carboxylic acid or cyclopentane carboxylic acid. Examples of aromatic carboxylic acids are benzoic acid, salicylic acid or cinnamic acid. Examples of dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebatic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid. R1 is hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, methyl ethyl, or C00-(CrCi2)alkyl; and one of the R12 is hydrogen and the other is methyl. Especially preferred is a compound of formula Ilia. Specifically prefen-ed compounds are listed in Tables 1, 2 and 3. Table 1 1.)2,6-Diethyl-4.4-dimethoxy-2,3,6-trimethyl-1-[1-(4-Oxiranyimethoxy-phenyl)-ethoxy]-piperidine 50 2,6-Diethyl-4,4-diisobutoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)ethoxy]-piperidine 6.) 2.6-Diethyl-2,3.6-trimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyI)-ethoxy^ piperidine 90 4,4-Bis-benzyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-ph piperidine 140 2-Butyl-7,9-diethyl-67.9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)ethoxyl}-1,4-dioxa-8-aza-spiro[4.5]decane 19.) Acetic acid 7,9-diethyl-67,9-trirnethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-yimethyl ester 20.) Octadecanoic acid 7,9-diethyl-6,7.9-trimethyl-8-I1-(4-Oxiranylmethoxy-phenyi)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester 240 2-Benzyloxymethyl-7,9-diethyl-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-ph 1.4-dioxa-8-aza-spiro[4.5]decane 25.) Octanedioic acid biS-{7.9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl} ester 28.)7,9-Diethyl-2,2,67,9-pentamethyl-841-(4-oxiranylmethoxy-phenyl)-ethox aza-spiro[4.5]decane 29.) 7,9-Diethyi-2,3,6,7,9-pentamethyl-8-[1 -(4-oxiranylmethoxy-phenyI)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane 330 8JO-Diethyl-7,8,10-trimethyl-9-[1-{4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa spiro[5.5]undecane 34.)8,10-Diethyl-3,37,8J0-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl}-ethoxy}-1,5-dioxa 9-a2a-spiro[5.5]undecane 38.)3-Butyl-3,8,10-triethyl-7,8J0-trimethyl-9-I1-(4-oxiranylmethoxy-ph dioxa-9-a2a-spiro[5.5]undecane 390 2.4-Diethyl-1,2.4-trimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy}-7,16-dioxa-3-aza dispiro[5.2.5.2]hexadec-11-ene 44.) 3-Benzyloxymethyl-8,10-diethyl-37,8.10-tetramethyl-9-[1-(4-oxiranyImethoxy ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 480 8,1O-Diethyl-3,7,8.10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-rthoxy}-1m5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylic acid methyl ester 490 8,1O-Diethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-etho^^^ spiro[5.5]undecane-3.3-dicarboxylic acid diethyl ester Table 2 10 2.2-Diethyl-4,,4-dimethoxy-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-pheny^ piperidine 6.) 2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy'1-[1-(4-ox!ranyimethoxy-phenyl)-ethoxy]-piperidine 11.) 7J-Diethyl-2,9,9-trimethyl-8-[1-(4-oxiranylnfiethoxy-phenyl)-ethoxy]1,4-dioxa-8-aza spiro[4.5]decane 150 77-Diethyl-9,9-iimethy!-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy}-1m4-dioxa-8-aza-spiro[4.5]decane 20.) Octadecanoic acid 77-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester 240 2-Ben2yloxymethyl-77-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-eth dioxa-8-aza-spiro[4.5]decane 25.) Octanedioic acid bis-{77-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl} ester 280 77-Diethyl'2,2,9,9-tetramethyl-841-(4-oxiranylmethoxy-phenyl)-eth spiro[4.5]decane 33.) 8,8-Diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 380 3-Butyl-3,8,8-triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phen 9-aza-spiro[5.5]undecane 43.)3-Cyclohexyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmeth ethoxy]-1,5-dioxa-9-a2a-spiro[5.5]undecane 47.) 1\6'-Bis-{3,8,8-triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-etho dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane 48.) 8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-^ spiro[5.5]undecane-3-carboxylic acid methyl ester 51.) 2,2-Diethyl-4,4-dimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-a2a-spiro[5.6]dodec-9-ene Table 3 1.) 4,4-Dimethoxy-2,2,6,6-tetramethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 5.) 4,4-Diisobutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine nyI)-ethoxy]-piperidine 70 4,4-Bis-aIlyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidi^ 9.) 4,4-Bis-ben2yloxy-2,2,6,6-tetramethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 15.) 7,7,9,9-Tetramethyl-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane 20.) Octadecanoic acid 7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester 24.) 2-Ben2yloxymethyl-7,7,9,9-etramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,^ dioxa-8-a2a-spiro[4.5]decane 28.) 2,277,9,9-Hexamethyl-8-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-1,4-dioxa-^^^ spiro[4.5]decane 290 2.37.7,9,9-Hexamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-diox^^^ spiro[4.5]decane 38.) 3-Butyl-3-ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-pheny!)-ethoxy^ 9-aza-spiro[5.5]undecane 43.) 3-Cyclohexyloxymethyl-3,8.8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-pheny^ ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 480 3,8,810,1O-Pentamethyl-9-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-1,5-diox spiro[5.5]undecane-3-carboxylic acid methyl ester Particularly preferred are the following compounds: 4,4-Dibutoxy-2,6-diethyl-2,3,6-trirnethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-p^ 7.9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-^ spiro[4.5]decane 77-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]decane 7,7,9.9-Tetramethy!-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5)decane A further subject of the invention is a polymerizable composition, comprising a) at least one ethylenically unsaturated monomer or oligomer, and b) a compound of formula la, lla or Ilia Ri3 is phenyl or CrCiealkyI; m is 1, 2 or 3; n is 1 or 2; if n is 1 Y and Y* are independently C1-C12alkyl, C3-C12alkenyl, C3-C12alkinyl, Cs-CBcycloalkyI, phenyl, naphthyl, Cr-Cophenylalkyl; or Y and Y' together form one of the bivalent groups -C(Ri)(R2)-CH(R3)-, CH(Ri)-CH2- C(R2)(R3)-. -CH(R2)-CH2-C(Ri)(R3)-, -CH2-C(Ri)(R2)-CH(R3h o-phenylene, 1,2- cyclohexyliden, Definitions and preferences have already been given above for the compounds. They apply also for the composition. The monomers suitable for use in the present invention may be water-soluble or water-insoluble. Water soluble monomers contain typically a salt of a carboxylic acid group. Water insoluble monomers are typically free of acid and phenolic groups. Typical metal atoms are Na, K or Li. Typical monoethylenically unsaturated monomers free of carboxylic acid and phenolic groups which are suitable for this invention include the alkyl esters of acrylic or methacrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate; the hydroxyalkyi esters of acrylic or methacrylic acids, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide, methacrylamide, N-tertiary butylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide; acrylonitrile, methacrylo-nitrile, allyl alcohol, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, vinyl acetate, conjugated dienes such as butadiene or isoprene, styrene, styrenesulfonic acid salts, vinylsulfonic acid salts and 2-acrylamidO-2-methylpropane-sulfonic acid salts and acryloil chloride. Preferred ethylenically unsaturated monomers or oligomers are selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides. Particularly preferred ethylenically unsaturated monomers are styrene. a-methyl styrene, p-methyl styrene, butadiene, methylacrylate, ethylacrylate, propyjacrylate, n-butyl acrylate, tert.-butyl acrylate and acrylnitril. In a most preferred composition the ethylenically unsaturated monomer is styrene. Preferred acrylates are methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butyiacrylate, hydroxyethylacrylate. hydroxypropylacrylate, dimethylaminoethyiacryjate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate. butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate. glycidyl(meth)acryiates, acrylonitrile, acrylamide or methacrylamide. Examples for C8-C16 ethylenically unsaturated phenolics, which may also be used as comonomers include 4-hydroxy styrene, 4-hydroxy-a-methyl styrene, and 2,6-ditert, butyl, 4-vinyl phenol. Another class of carboxylic acid monomers suitable for use as comonomers in this invention are the alkali metal and ammonium salts of C4-C6-ethylenically unsaturated dicarboxylic acids. Suitable examples include maleic acid, maleic anhydride, itaconic acid, mesaconic acid, fumaric acid and citraconic acid. Maleic anhydride (and itaconic acid are) is the preferred monoethylenically unsaturated dicarboxylic acid monomer(s). The acid monomers suitable for use in this invention are in the form of the alkali metal salts or ammonium salts of the acid. The polymerizable composition of the present invention may additionally comprise a solvent selected from the group consisting of water, alcohols, esters, ethers, ketones, amides, sulfoxides, hydrocarbons and halogenated hydrocarbons. The invention also relates to a free radical polymerization process and polymers obtained thereby, which process overcomes many of the problems and disadvantages of the afore mentioned prior art processes. Preferably the initiator compound is present in an amount of from 0.01 mol-% to 20 mol-% , more preferably in an amount of from 0.01 mol-% to 10 mol-% and most preferred in an amount of from 0.05 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 of formula la, lla or Ilia under reaction conditions capable of effecting scission of the 0-C bond to form two The process may be carried out in the presence of 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. Prefen-ed 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 prefen-ably 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), halogenated 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 homogeneous single phase throughout the monomer 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, pyn-olidines, N-alkyI pyn-olidinones, 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 cellosolve, 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. When monomer mixtures or monomer/oligomer mixtures are used, the calculation of mol-% is based on an average molecular weight of the mixture. Hydrophilic monomers, polymers and copolymers of the present invention can be separated from one another or from the polymerization reaction mixture by, for example, changing the pH of the reaction media and by other well known conventional separation techniques. The polymerization temperature may range from about 50°C to about 180°C, preferably from about 80°C to about 150°C. At temperatures above about 180°G, the controlled conversion of the monomer into polymer decreases, and uncertain and undesirable by-products like thermally initiated polymer are formed or destruction of the polymerization regulator may occur. Frequently, these by-products discolor the polymer mixture and a purification step may be required to remove them, or they may be intractable. Therefore high reactivity of the present initiators which are already active at relatively low temperatures leads to short reaction times. The resulting polymers are usually colouriess and they can be used in most cases without any further purification step. This is an important advantage when industrial scale-up is considered. After the polymerizing step is complete, the formed (co)polymer obtained is isolated. The isolating step of the present process is conducted by known procedures, e.g. by distilling off the unreacted monomer or by precipitation in a suitable nonsolvent, filtering the precipitated polymer followed by washing and drying the polymer. 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. The (co)polymers of the present invention may have a number average molecular weight from 1 000 to 400 000 g/mol, preferably from 2 000 to 250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mo1. When produced in bulk, the number average molecular weight may be up to 500 000 (with the same minimum weights as mentioned above). The number average molecular weight may be determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC), matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) or, if the initiator carries a group which can be easily distinguished from the monomer(s), by NMR spectroscopy or other conventional methods. Thus, the present invention also encompasses in the synthesis novel block, multi-block, star, gradient, random, hyperbranched and dendritic copolymers, as welf as graft or copolymers. The polymers prepared by the present invention are useful for example in following applications: adhesives. detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, impact modifiers, thickeners, crosslinkers, paper treatment, water treatment, electronic materials, paints, coatings, photography, ink materials, imaging materials, superabsorbants, cosmetics, hair products, preservatives, 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 will. Furthermore, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymerization in a living matter. Thus, in one embodiment of this invention, once the first monomer is consumed in the initial polymerizing step a second monomer 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 order. One is not necessarily restricted to preparing block copolymers where the sequential polymerizing 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 possible to prepare a multi-block copolymer in which a polyacrylonitrile or a poly(meth)-acrylate block is prepared first, then a styrene or butadiene block is attached thereto, and so on. Furthermore, there is no linking group required for joining the different blocks of the present block copolymer. One can simply add successive monomers to form successive blocks. A plurality of specifically designed polymers and copolymers are accessible by the present invention, such as star and graft (co)polymers as described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107, pages 1623-1627, dendrimers as described by K. Matyaszewski et al. in Macromolecules 1996, Vol 29, No. 12, pages 4167-4171, graft (co)polymers as described by C. J. Hawker et al. in Macromol. Chem. Phys. 198, 155-166(1997), random copolymers as described by C. J. Hawker in Macromolecules 1996, 29, 2686-2688, or Also subject of the invention is the use of a compound of formula la, ila or Ilia for terminating the anionic polymerization of a diene or vinyl monomer. When the compounds are used for such termination reactions they are usually used in an -equimolar amount or in excess to the initiating base, such as for example sec. butyl-litium. The preparation of the compounds of the present invention is carried out according to known reaction steps. A general method for the preparation of the compounds of formula la, Ila, and Ilia starts from the 4-oxo compounds Xa or Xla which are described in GB 2335190 or from Xlla which is a known compound described for example in DE 2352127. The compounds of formula Xb, Xlb and Xllb are oxidized according to standard procedures to the corresponding nitroxides of formula Xc, Xlc and Xllc, as for example described in GB 2335190 or WO 99/46261. formula la, lla or Ilia. This coupling reaction is also descriebed for example in GB 2335190 or in WO 99/46261. Preferably the coupling reaction is carried out in the presence of a Cu(ll) salt according to the method described in International Application No. PCT/EP01/05668. These compounds are novel and consequently are also subject of the present invention. The above given definitions and preferences apply also for the compounds of formula Xd, Xld and Xlld. The compounds of formula Xd, Xld and Xlld can be reacted with epichlorohydrine and compounds according to formula la, lla or Ilia are obtained. The following examples illustrate the invention. Preparation of an intermediate according to formula Xlld. A mixture of 25,6 g 3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (prepared according to EP 574666A1) and 82,1 g acetic acid 4-ethyl-phenyl ester are heated to 50°C with stirring and 0,68 ml of an ethanolic solution containing 0,13 g copper(ll)chloride is added. The temperature, is raised to 65°C and 19,4 g of an aqueous solution of butylhydroperoxide in water (70%) are dropwise added. The reaction mixture is allowed to further react for 22h at 65°- 70°C and subsequently cooled to room temperature. Excess tert.-butylhydroperoxide is removed by dropwise adding 4m! of an aqueous sodium pyrosulfite solution (20%). To the reaction mixture 5Dml acetic acid ethylester are added and the organic and aqueous phase are separated. The organic phase is washed with a saturated NaCI solution. After drying with sodium sulfate and evaporation of the solvent an oil is obtained, from which excess acetic acid 4-ethyl-phenyl ester is removed by distillation (100°C/0,025 mbar). The residue is dissolved in methanol/hexane (4/1 by volume) on heating to refux. After cooling to 0°C the precipitate is filtered off. After recrystalization from acetone white crystals are obtained having a melting point of 124 -125°C. A mixture of 8 g acetic acid 4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-a2a-spiro[5.5]undec-9-yloxy)-ethyl]-phenyl ester and 3,9 g potassium carbonate in 60 ml methanol is stirred for one hour at room temperature. The mixture is cooled to O°C and neutralized by adding 60 ml of 0.5 M hydrochloric acid. The white suspension is diluted with water (60 ml) and filtered through a buchner funnel. The residue is washed with water and dried in a vacuum oven at SOX. A white solid having a melting point of 133 - 134°C is obtained. A mixture of 50 g 7,7,9.9-tetramethyl-1,4-dioxa-8-a2a-spiro[4.5]decan-8-oxyl (prepared according to EP 574666A1) and 124,75 g 2-(4-ethyl-phenoxymethyl)-oxiran are heated to 60** C with stirring and a solution of 0,32 g copper(ll)chloride in 1,6 ml ethanol is added. 45 g of an aqueous solution of butylhydroperoxide in water (70%) is dropwise added. The reaction mixture is allowed to further react for 16h at 60° C and subsequently cooled to room temperature. Excess tert.-butylhydroperoxide is removed by dropwise adding 15ml of an aqueous sodium pyrosulfite solution. To the reaction mixture 100ml acetic acid ethylester are added and the organic and aqueous phase are separated. The organic phase is washed twice with 200 ml of a saturated NaCI solution. After drying with sodium sulfate and evaporation of the solvent an oil is obtained, from which excess 2-(4-ethyl-phenoxymethyl)-oxiran is removed by distillation (100°C/0,005 mbar). The residue is dissolved in hexane filtered over aluminium oxide and the solvent is again evaporated. After recrystalization from hexane white crystals are obtained having a melting point of 73.5-74.2' C. The title compound is prepared in analogy to example A1 from 3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (prepared according to EP 574666A1). White crystals are obtained. Elemental analysis: calculated: 69.25% C; 9,07% H; 3,23% N; found:68,86% C; 9,05% H; 3.18% N. A mixture of 50 g 3,3,8,8,10,10-hexamethyl-l.5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (CAS 98254-32-1) and 41 g (4-Ethyl-phenyl)-phenyl-methanone (preparation by Friedel-Crafts acylation of 4-ethylben2ene with benzoylchloride) is heated to 60'C and a solution of 0,26 g copper(ll)chloride in 1,3 ml ethanol is added. 53,7 g of a 70% aqueous solution of tert-butylhydroperoxide in water are added dropwise. The reaction mixture is allowed to further react for 28 h and subsequently cooled to room temperature. Excess tert-butylhydroperoxide is then removed by dropwise adding an aqueous solution of sodium pyrosulfite. To the reaction mixture 100 ml of ethyl acetate are added and the organic phase is separeted from the aqueous phase. The organic phase is washed twice with water (200 ml) and the solvent evaporated. The residue is purified chromatographicaliy on silica gel with hexane/ethyl acetate (7:3 by volume) as the eluente. After recrystaliization from pentane/ethanol (5:3 by volume) white crystals of a compound of formula are obtained having a melting range of 104 - 117°C. 'H-NMR (300 MHz; 5 in ppm; CDCI3): 0,7 (s broad, 3 H); 0,94 (s broad, 6 H); 1,18 (s broad. 3 H); 1.33 (s broad, 6 H); 1.51.1.53 (d, 3 H); 1,4-1,65 (m. 2 H); 2-2.25 (m. 2 H); 3.46 (s broad, 4 H); 4,84-4.91 (q. 1 H); 7.4-7,9 (aromatic H. 9 H). Example A19: 8.8-Diethvl-3.3.10,10'tetramethvl-9'f1-(4-oxiranvlmethQxv-phenvl)-ethoxv1-1.5-dioxa-9-aza-spirof5.51undecane To a stirred mixture of 25.6 g 8,8-diethyl-3.3,10,10-tetramethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl and 80,2 g 2-(4-ethyl-phenoxymethyl)-oxirane at 50°C is added a solution of 0,12 g copper(ll)chloride in 0,6 ml ethanol. The temperature of the reaction mixture is increased to 70°C and 11.6 g of a 70% aqueous solution of tert-butylhydroperoxide in water are added dropwise. The reaction mixture is allowed to further react for 6 h at 70°C and subsequently cooled to room temperature. Excess tert-butylhydroperoxide is removed by dropwise adding an aqueous solution of sodium pyrosulfite (2 ml). To the reaction mixture 50 ml of ethyl acetate and 50 ml 10% aqueous solution of sodium chloride are added. The mixture is filtered through celite and the organic phase is separeted. The organic phase is washed three times with 10% aqueous solution of sodium chloride (100 ml) and dried over sodium sulfate. After evaporation of the solvent an oil is obtained, from which excess 2-(4-ethyl-phenoxymethyl)-oxirane is removed by distillation (80°C, 0,025 mbar). A highly viscous residue is obtained which crystallises on standing at room temperature. After recrystaliization twice from methanol white crystals of To a stirred mixture of 59,7 g 8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl and 178,2 g 2-(4-ethyi-phenoxymethyl)-oxirane a solution of 0,27 g copper(ll)chloride in 1,35 ml ethanol is added at about 60°C. Then 38.7 g of a 70% aqueous solution of tert-butylhydroperoxide in water are added dropwise. An exothermic reaction started and the temperature is kept at 70°C. The reaction mixture is allowed to further react ■ for 24 h at 70°C and subsequently cooled to room temperature. The reaction mixture is diluted with 100 ml of ethyl acetate. Excess tert-butylhydroperoxide is removed by dropwise adding an aqueous solution of sodium pyrosuifite (70 ml) below 20°C. The organic phase is separeted, washed twice with 10% aqueous solution of sodium chloride (100 ml) and dried over sodium sulfate. After evaporation of the solvent an oil is obtained, from which excess Z- (4-ethyl-phenoxymethyl)-oxirane is removed by distillation (80°C, 0,025 mbar). A highly viscous resin degassed in three consecutive freeze-thaw-cycles and then purged with argon. The stirred solution is then immersed in an oil bath and polymerized at the given temperature for 6 hours. After polymerization, residual monomer is removed under vacuum at 60°C and the polymer is dried at 60°C in vacuo until constant weight is achieved. Molecular weight and molecular weight distributions are determined by size exclusion chromatography (SEC) on a HP 1090 liquid chromatograph (software: winGPC / Polymer Standard Services, Mainz, Germany) using THF as eluent and a column combination calibrated with narrow polystyrene standards (Polymer Laboratories). The results are given in Table 1. Polymerization with n-BuA Example B7 n-Butylacrylate is destilled under reduced pressure prior to use. In a dry, argon-purged Schlenk tube, the amounts of nitroxyl ether given in Table A are dissolved in 62.5 ml n-butylacrylate. The solution is degassed in three consecutive freeze-thaw-cycles and then purged with argon. The stirred solution is then immersed in an oil bath and polymerized at 130°C for 6 hours. After polymerization, residual monomer is removed under vacuum at 30°C and the polymer is dried at 30°C in vacuum until constant weight is achieved. Molecular weight and molecular weight distributions are determined by size exclusion chromatography (SEC) on a HP 1090 liquid chromatograph (software: winGPC / Polymer Standard Services, Mainz, Germany) using THF as eluent and a column combination calibrated with narrow polystyrene standards (Polymer Laboratories). The results are giva§ in Table 7. Example B8: Anionic polymerization and termination of isoprene with the compound of example A2 To 10.2 g (0.15 mol) isoprene dissolved in 50 ml dry toluene in a dried ampule with teflon valve equipped with a magnetic stir bar are added in a dry argon atmosphere 3,34 x 10'^ mol sec.-butyllithium (1.3 mol/L solution in cyclohexane, Fluka) and stirred for 18 hours at room temperature to allow polymerization. Subsequently a sample of the resulting prepolymer is drawn via syringe, dried at room temperature in vacuo and submitted to GPC. To the residual, slightly yellow polyisoprene solution is slowly added a calculated amount of the compound of example A2 (1.2 and 1.5 fold molar excess with respect to the initial molar amount of sec.-butyllithium used) (dissolved in toluene and degassed) via syringe. The mixture is allowed to react for another 6 hours at room temperature. Subsequently the termination reaction is quenched adding a few ml of degassed methanol. Volatiles are removed in vacuo and the resulting polyisoprene is obtained as a slight yellow rubber after drying at room temperature in vacuo until constant weight is achieved. Molecular weights are determined by GPC on a HP 1090 equipped with a Rl and DAAD (set at 254 nm) detector with THF as efuent (1 ml/min), using PS standards for calibration. R13 is phenyl or C1-C18alkyl; m is 1, 2 or 3; n is 1 or 2; if n is 1 Y and Y' are independently C1-C12alkyl, C3-C12alkeny!, C3-C12alkinyl, Cs-Cecycloalkyl, phenyl, naphthyl, Cr-CsphenylalkyI; or Y and r together form one of the bivalent groups -C(Ri)(R2)-CH(R3)-, CH(Ri)-CH2-C(R2)(R3)-, -CH(R2)-CH2-C(Ri)(R3)-. -CH2-C(R1)(R2)-CH(R3)-, o-phenylene, 1,2-cyclohexyliden, R4 is hydrogen. C1-C12alkyl, benzyl, or a monovalent acyl residue derived from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid having up to 18 carbon atoms; if n is 2 Y and Y' together form one of the tetravalent groups Y and Y' together form one of the bivalent groups -C(R1)(R2)-CH(R3)-. CH(R1)-CH2- C(R2)(R3K -CH(R2)-CH2-C(Ri)(R3)-. -CH2-C(R1)(R2^CH(R3)^ -CH2-CH=CH-CH2- or wherein Ri is hydrogen, CrCi2alkyl. C00-(Ci-Ci2)alkyl or CH2OR4; R2 and R3 are independently hydrogen, methyl ethyl, or C00-(C1-C12)alkyl; R4 is hydrogen, C1-C12alkyl, benzyl, or a monovalent acyl residue derived from an aliphatic, cycloaliphatic or aromatic monocarboxylic acid having up to 12 carbon atoms and one of the R12 is hydrogen and the other is methyl. m is1; n is 1 ; Y and Y' together form one of the bivalent groups -CH2-C(Ri)(R2)-CH(R3)- wherein Ri is hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, methyl ethyl, or C00-(CrCi2)alkyl; and one of the R12 is hydrogen and the other is methyl. 5. A compound according to claim 1 which is of formula Ilia. 6. A compound according to claim 1 of formula la, lla or Ilia which is 1.) 2,6-Diethyl-4,4-dimethoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 2.)4,4-Diethoxy-2,6-diethyl-2.3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 3.)2,6-Diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxyH,4-dipropoxy- piperidine 4.)4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 5.)2,6-Diethyl-4,4-diisobutoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 6.) 2,6-Diethyl-2,3.6-trimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy}- piperidine 70 4,4-Bis-allyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 8.) 4,4-Bis-cyclohexyloxy-2,5-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-eth piperidine 90 4,4-Bis-benzyloxy-2.6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 10.) 7,9-Diethyl-6J.9-trJmethyl-8-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane 11.) 7,9-DiethyI-2,6,7,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane 12.) 2J,9-Triethyi-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza spiro[4.5]decane 13.) 7,9-Diethyl-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyl-1,4-dioxa-8- a2a-spiro[4.5]decane 14.) 2-Butyl-7,9-diethyl-6J,94rimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-di aza-spiro[4.5]decane 15.)7,9-Diethyl-6J,9-trimethyi-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8- a2a-spiro[4.5]decane 16.) 2-Decyi-7.9-diethyl-6J,9-trimethyl-8-[1-(4-Oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8- a2a-spiro[4.5]decane 17.) 2-Dodecyl-7,9-diethyl-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4 8-a2a-spiro[4.5]decane 18.){7,9-Diethyl-67,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza spiro[4.5]dec-2-yl}-melhanol 19.) Acetic acid 7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranytmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester 20.) Octadecanoic acid 7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- 1.4-dioxa-8-aza-spiro[4,5]dec-2-y!methyl ester 21.) Benzoic acid 7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-aza-spiro[4.5]dec-2-ylmethyl ester 22.) 7,9-Diethyl-2-nriethoxymethyl-6,7,9-trimethyl-8-I1-(4-oxiranylnriethoxy-phenyl)-ethoxy]- 1,4-dioxa-8-aza-spiro[4.5]decane 230 2-Cyclohexyloxymethyl-7.9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phen ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane 24.) 2-Benzyloxymethyl-7,9-diethy!-6,7,9-trimethyl-8-1-(4-oxiranylmethoxy-phenyl)-ethoxy]- 1,4-dioxa-8-a2a-spiro[4.5]decane 25.) Octanedioic acid bis-{7,9-diethyl-6.7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)- ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]deC-2-ylmethyl} ester 26.) Terephthalic acid bis-{7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)- ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyi} ester 27.) 1\4-Bis-{7,9-diethyl-67.9-trimethyl-8-(1-(4-oxiranylmethoxy-phenyl)-ethoxy)-1,^ 8-a2a-spiro[4 28.)7.9-Diethyl-2,2,6J,9-pentamethyl-841-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa^^^ aza-spiro[4.5]decane 290 7,9-Diethyi-2,3,67,9-pentamethyl-8-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-1,4-dioxa-8-- aza-spiro[4.5]decane 30.) 4,4-(o-Phenylendioxy)-2,6-diethyl-2,3,6-trimethyl-1-[V-(4'-oxiranylmethoxy-phenyl)- ethoxyj-piperidine 31.)4.4-(1\2'-cyclohexylendioxy)-2,6-diethyl-2,3,6-trimethyl-1-[r'-(4'-oxiranylmethoxy- phenyl)-ethoxy]-piperidine 320 7.9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane-2,3-dicarboxylic acid dimethyl ester 33.) 8,10-Diethyl-7,8J0-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane 34.)8,10-Diethyl-3,3,7,8,10-pentamethyl-9-1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa- 9-aza-spiro[5.5]undecane 35.)3,8J0-Triethyl-3,7,8,10-tetramethyl-9-[1-(4-oxirany!methoxy-phenyi)-ethoxy]-1,5'di 9-aza-spiro[5.5]undecane 36.) 3.3,8J0-Tetraethyl-7,8J0-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa- 9-aza-Spiro[5.5]undecane 37.) 8JO-Diethyl-3J,8JO-tetramethyl-9-[1-(4-oxiranylrnethoxy-phenyi)-ethoxy]-3-propyl-1,5- dioxa-9-aza-spiro[5.5]undecane 380 3-Butyl-3,8,10-triethyl-7,8,10-trirnethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5 diGxa-9-aza-spiro[5.5]undecane 39.)2,4-Diethyl-1,2,44rinriethyt-3-[1-{4-oxiranylrneihoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza- dispiro[5.2.5.2]hexadec-11-ene 40.){8,10-Diethyl-3,7,8.10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]1,5-dioxa-9- aza-spiro[5.5]undec3-yl}-methanol 410{3.8,10-Tnethyl-7.8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethyoxy]-1m5-dioxa-9- aza-spiro[5.5]undec-3-yl}-methanol 42.) 8.10-Diethyl-3-methoxymethyl-3J,8J0-tetramethyl-9-[1-(4-oxiranyimethoxy-phenyl)- ethoxy]-1,5-dioxa-9-aza-spiro[5,5]undecane 43.) 3-CyclohexyIoxymethyl-8,10-diethyi-3,7,8J0-tetramethyl-9-[1-(4-oxiranyImethoxy- phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 44.)3-Benzyloxymethyl-8J0-diethyl-3J,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 45.) Acetic acid 8,10-diethyl-3J,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- 1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl ester 46.) Octanedioic acid bis-{8,10-diethyl-3J,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)- ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl} ester 47.) 1\6'-Bis-^3.8J0-triethyl-7,8J0-trimethyl-9-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1.5- dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane 48.)8J0-DJethyl-37,8J0-tetrarnethyl-9-[1-(4-oxiranylmethQxy-phenyl)-ethoxy]-1,5-dioxa-9- aza-spiro[5.5]undecane-3-carboxy!ic acid methyl ester 49.) 8J0-Diethyl-7,8J0-trirnethyl-9-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane-3,3-dicarboxylic acid diethyl ester 50.)33-Bis^8,10-diethyl-7,8,104rimethyl-9-[1-(4--oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-- 9-aza}-spiro[5.5]undecane 51.)2,4-Diethyl-1,2,4-trimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3'aza- spiro[5.6]dodec-9-ene 52.) 2,2-Diethyi-4,4-dimethoxy-6.6-dimethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 530 4,4-Diethoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 54.) 2,2-Diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-4,4-dipropoxy- piperidine 55.)4,4-Dibutoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 56.) 2,2-D!ethyl-4,4-diisobutoxy-6,6-dimethyl-1 -[1 -(4-Oxiranylmethoxy-phenyl)-ethoxy]- piperidine 57.)2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-eihoxy]- piperidine 58.)4,4-Bis-allyloxy-2,2-diethyl-6,6-dimethyl-1-[1-{4-oxiranylmethoxy-phenyI)-etho piperidine 59.) 4,4-Bis-cyclohexyloxy-2,2-diethyl-6,6-dimethy!-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 60.)4,4-Bis-benzyloxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-pheny!)-ethoxy]- piperidine 61.) 77-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyi)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 62.) 7,7-Diethy!-'2,9,9-trimethy!-8-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane 63.) 2.7 J-Triethyl-9,9-dimethyl-8-[1 -(4-oxiranylmethoxy-phenyI)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 64.)7J-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyI)-ethoxy]-2-pra^ a2a-spiro[4.5]decane 650 2-Butyl-77-diethy(-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1^ a2a-spiro[4.5]decane 66.) 77-Dtethyl-9,9-dimethyl-2-octyl-8-[1-(4-oxirany!methoxy-phenyl)-ethoxy]-1,4-d aza-spiro[4.5]decane 67.)2-Decyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8- a2a-spiro[4.5]decane 680 2-Dodecy)-77-diethyl-9,9-dimethyl-841-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-diox a2a-spiro[4.5]decane 690{77-Diethyl'9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]dec-2-y(}-methanol 70.) Acetic acid 7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa- 8-aza-spiro[4.5]dec-2-ylmethyl ester 71.) Octadecanoic acid 7,7-diethy(-9.9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.4- dioxa-8-a2a-spiro[4.5]dec-2-ylmethyI ester 72.) Ben2oic acid 7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa- 8-a2a-spiro[4.5]dec-2-ylniethyl ester 73.) 77-Diethyl-2-methoxymethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-a2a-spiro[4.5]decane 74.) 2-Cyclohexyloxymethyl-77-diethyl-9,9-d(methyl-8-[1-(4-oxiranylrnethoxy-phenyl)- ethoxy]-1,4-d!oxa-8-a2a-spiro[4.5]decane 75.) 2-Benzyloxymethyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-a2a-spiro[4.5]decane 76.) Octanedioic acid bis-{7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- 1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl} ester 77.) Terephthalic acid bis-{7,7-diethyl-9,9-dimetlnyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- 1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl} ester 78.) 1\4'-Bis-{7,7-diethyl-9,9-diniethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8- aza-spiro[4,5]dec-2-ylmethyl}-oxybutane 79.) 7,7-Diethyl-2,2.9,9-tetramethyl-8-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 80.) 7J-Diethyl-2,3,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 81.)4,4-(o-Phenylendioxy)-2,2-diethyl-6,6-dimethyl-1-[1'-(4'-oxiranylmethoxy-phenyl)- ethoxy]-piperidine 82.)4,4-(1\2'-cydohexyiendioxy)-2,2-diethyl-6,6-dimethyl-1-[1'(4'-oxiranylmethoxy-ph ethoxy]-piperidine 83.) 7,7-Diethyl-9,9-dimethyl-8-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane-2,3-dicarboxylic acid dimethyl ester 84.) 8,8-Diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-9-aza- spJro[5.5]undecane 85.) 8,8-Diethyl-3,3J0J0-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9- aza-spiro[5.5]undecane 86.)3,8,8-Triethyl-3.10J0-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dio^^^ aza-spiro[5.5]undecane 87.)3,3,8,8-Tetraethyi-10,10-dimethyl-9-[1-(4-oxiranylrriethoxy-phenyl)-ethoxy]-1,5-dicxa-9- • aza-spiro[5.5]undecane 88.)8,8-Diethyl-3,10,10-trimethyl-941-(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-^ dioxa-9-aza-spiro[5.5]undecane 89.)3-Butyl-3,8,8-triethyl-10J0-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethaxy]-1.5-dioxa- 9-a2a-spiro[5.5]undecane 90.)2.2-Diethyl,4-dimethyl-3-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza- dispiro[5.2.5.2]hexadec-11-ene 910{8,8-Diethyl-3,10,10-trimethyl'-[1-(4-oxiranylmethoxy-phenyl)-ethGxy]-1,5-d^ spiro[5.5]undec-3-yl}-methanol 92.) {3,8,8-Triethyl-10.10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-^ spiro[5.5]undec-3-yl-methanol 93.) 8,8-Diethyl-3-methoxymethyl-3,10,10-trimethy!-9-[1-(4-oxiranylmethoxy-phenyl)-^^^ 1,5-dioxa-9-aza-spiro[5.5]undecane 94.) 3-Cyclohexyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranyImethoxy-phe ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 95.) 3-Benzyloxymethyl-8,8-diethyl-3,10,10-rirnethyl-9-[1-(4-oxiranylmethoxy-phenyl)- ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane 96.) Acetic acid 8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5- dioxa-9-aza-spiro[5.5]undec-3-yimethyl ester 97.) Octanedioic acid bis-{8,8-diethyl-3,10,10-trimethyl-9-[1-(4-Gxiranylmethoxy-phenyl)- ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl} ester 98.) 1\6'-Bis-{3,8,8-triethyl-10,10-dimethyl-9-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5- dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane 99.) 8,8-Diethyl-3,10J0-trimethyl-941-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane-3-carboxylic acid methyl ester 100.) 8,8-D!ethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane-3,3-dicarboxylic acid diethyl ester 101.)3,3-Bis-{8.8-diethyl-10,10-dimethyl-9-[1-(4--oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa- 9-aza}-spiro[5.5]undecane 102.)2,2-Diethyl-4.4-dimethyl-3-[1-(4-oxiranylniethoxy-phenyl)-ethoxy]-7J2-dioxa-3-aza^ spiro[5.6]dodec-9-ene 103.)4,4-Dimethoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 104.) 4,4-Diethoxy-2,2,6,6-tetramethyl-1-[1-(4-OXiranylmethoxy-phenyI)-ethoxy]-piperidine 105.) 2,2,6,6-Tetramethy!-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxyH,4-dipropoxy-piperidine 106.)4,4-Dibutoxy-2,2,6,6-tetramethyI-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 107.)4,4-Diisobutoxy-2.2,6,6-tetramethy!-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine 108.) 2,2,6,6-Tetramethyl-4,4-bis-octyloxy-1-[1-(4-oxirany!methoxy-phenyl)-ethoxy]- piperidine 109.)4,4-Bis-allyloxy-2,2,6,6-tetramethyi-1-[1-(4-oxiranylmethoxy--phenyl)-ethoxy]-piperidine 110.) 4.4-Bis-cyclohexyloxy-2,2,6,6-tetramethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]- piperidine 111.)4,4-Bis-benzyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]- pipendine 112.) 77,9,9-Tetramethyl-8-I1--(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 113.) 2,7,7,9,9-Pentamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.4-dioxa-8-a2a- spiro[4.5]decane 114.) 2-Ethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 115.) 7.7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyi-1,4-dioxa-8-aza- spiro[4.5]decane 116.) 2-Butyl-7J,9,9-tetramethyl-8-[1-(4'Oxiranylrnethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane 117.)7,7.9,9-Tetramettyl-2-octyl-841-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-d spiro[4.5]decane 118.) 2-Decyi-77,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane 119.) 2-Dodecyl-7,7,9,9-tetramethyl-8-[1 -(4-oxiranylmethoxy-phenyI)-ethoxy]-1,4-dioxa-8- aza- spiro[4.5]decane 120.){7J,9,9-Tetramethyl-8-[1--(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]dec-2-yl}-methanol 121) Acetic acid 7J,9,9-tetramethyl-8-[1-(4-oxJranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8- aza-spiro[4.5]dec-2-ylmethyl ester 122.) Octadecanoic acid 7,7.9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-aza-spiro[4.5]dec-2-ylmethyI ester 123.) Benzoic acid 7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8- aza-spiro[4.5]dec-2-ylmethyl ester 124.) 2-Methoxyrnethyl-7J,9,9-tetrarnethyl-8--[1-{4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-aza-spiro[4.5]decane 125.)2-Cyclohexyloxyrnethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]- 1,4-dioxa-8-aza-spiro[4.5]decane 126.) 2-Benzyloxymethyl-7,7,9,9--tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-aza-spiro[4.5]decane 127.) Octanedioic acid bis-{7,7,9,9-tetramethyl-8-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dioxa-8-aza-spiro[4.5]dec-2-y!methyl} ester 128.) Terephthaiic acid bis-{7,7,9.9-tetramethyl-8-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4- dJoxa-8-aza-spiro[4.5]dec-2-ylmethyi} ester 129.) 1'4'-Bis-(77,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa"^^^ spiro[4.5]dec-2-yimethyl}-oxybutane 130.) 2,27,7,9.9-Hexamethyl-8-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane 131.) 2,3,7,7,9,9-Hexamethyl-8-[1-(4--oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa"8-a2a- spiro[4.5]decane 132.)4,4-(o-Phenylendioxy)-2,2,6,6-tetramethyl-1-[1'-(4'-oxiranylmethoxy-phenyl)-ethoxy]" piperidine 1330 4.4-(1\2'-cyclohexylendioxy)-2,2,6,6-tetramethyl-1-[r'-(4'-oxiranylmeth^^^^ ethoxy]-piperidine 134.) 77,9.9-Tetramethyl-8-[1-(4-oxiranylmethoxy--phenyl)-ethoxy]-1,4-dioxa-8-a2a- spiro[4.5]decane-2,3-dicarboxyiic acid dimethyl ester 135.) 8,8.10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-a2a- spiro[5.5]undecane 136.) 3,3,8.81,0,10-Hexamethyl'9-[1-(4-oxiranylmethoxy-phenyI)-ethoxy]-1.5-dioxa'9--a2a- spiro[5.5]undecane 137.) 3-Ethyl-3,8,8.10.10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-' a2a-spiro[5.5]undecane 138.)3,3-Diethyl-8,8,10,10-etramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9- a2a-spiro[5.5]undecane 139.) 3,8.8,10,10-Pentamethyl-9-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-1,5-dioxa-9- a2a-spiro[5.5]undecane 140.) 3-Butyl-3-ethyl-8,8,10,104etramethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,5- dioxa-9-a2a-spiro[5.5]undecane 141.) 2,2,4,4"Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza- dispiro[5.2.5.2]hexadec-11-ene 142.) {3,8,8,10,10-Pentamethyl-9-I1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dJoxa-9-aza- spiro[5.5]undec-3-yl}-methanol 143.){3-Ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9^ aza-spiro[5.5]undec-3-yl}-methanol 144.) 3-Methoxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]- 1,5-dioxa-9-a2a-spiro[5.5]undecane 145.)3-Cyclohexyloxymethyl-3,8,8,10,10-p6ntamethyl-9-[1-(4-oxiranylmethoxy-phenyl)^ ethoxy]-1,5"dioxa-9-a2a-spiro[5.5]undecene 146.)3-Benzyloxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy"phenyl)^^^ 1.5-dioxa-9-aza-spiro[5.5]undecane 147.) Acetic acid 3.8,8,10.10-pentamethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,5- dioxa-9-aza-spiro[5.5]undec-3-ylmethyl ester 148.) Octanedioic acid bis-{3,8,8,10,10-pentamethy!-9-[1-(4-oxiranylmethoxy"phenyl)- ethoxy]-1.5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl} ester 149.) 1\6'-Bis-{8.8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-9- aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane 150.) 3,8,8,10,10-Pentamethyi-9-[1 -(4-oxiranylmethoxy-phenyi)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane-3-carboxylic acid methyl ester 151.) 8,8,10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,5--dioxa-9-aza- spiro[5.5]undecane-3,3-dicarboxylic acid diethyl ester 1520 3,3-Bis-{8.8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9- aza}-spiro[5.5]undecane 153.) 2,2,4,4-Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-aza- spiro[5.6]d odec-9-ene 7. A compound according to claim 6 of formula la, lla or Ilia which is 4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]"piperidine; 7,9-Diethyi-67,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro- [4.5]decane; 8,10-Diethyl-3,3,7,8,10-pentamethyi-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9- aza-spiro[5.5]undecane; {8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undec-3-yl}-methanol; {3,8,10-Triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-9-aza-- spiro[5.5]undec-3-yl}-methanol; 4.4-Dibutoxy"2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy>piperidine; 7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,4-dioxa-8-aza- spiro[4.5]decane; 8,8-Diethyl-3,3,10,10-tetramethyl-9-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane; {8.8-Diethyl"3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undec-3-yl}-methanol; {3,8,8-Triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-di spiro[5.5]undec-3-yl}-methanol; 4,4-Dibutoxy-2,2,6,6-tetramethyl-141-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidin 7,7,9,9-Tetramethyl-8-[1-(4-oxiranyImethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a" spiro[4.5]decane; 3,3,8,8,10,10"Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza- spiro[5.5]undecane. Y and Y* together form one of the bivalent groups -C(R1)(R2)-CH(R3)-, CH(R1)-CH2-C(R2)(R3)". -CH(R2)-CH2-C(Ri)(R3)-. -CH2-C{R1)(R2)-CH(R3)-, o-phenylene, 1,2-cyclohexyliden, 9. A polymerizable composition according to claim 8, wherein the ethylenically unsaturated monomers or oligomers are selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides. 10. A polymerizable composition according to claim 9, wherein the ethylenically unsaturated monomers are styrene. a-methyl styrene, p-methyl styrene, butadiene, methylacrylate, ethylacrylate, propylacrylate, n-butyl acrylate. tert.-butyl acrylate and acrylnitrii. 11. A polymerizable composition according to claim 8. wherein the compound of formula la, Jia or Ilia is present in an amount of from 0.01 mol-% to 20 mol-% based on the monomer. 15. Use of a compound of formula la, lla or Ilia according to claim 1 for polymerizing ethylenically unsaturated monomers. 16. Use of a compound of formula la, lla or Ilia according to claim 1 for terminating the anionic polymerization of a diene or vinyl monomer. 18. A polymerizable composition substantially as herein described with reference to the accompanying drawings. 19. A process for preparing an oligomer substantially as herein described with reference to the accompanying drawings.

Full Text

N-ALK0Xy-4,4-DI0XY-P0LyALICYL-PIPERIDINES AS RADICAL POLYMERIZATION INITIATORS
The present invention relates to selected glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine compounds forming an open chain or cyclic ketal structure, a polymerizabie composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiator compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers and the use of glycidyl or carbonyl functional N-alkoxy-4,4-dioxy-polyalkyl-piperidine nitroxide initiators for radical polymerization.
The compounds of the present invention provide polymeric resin products having low polydispersity and the polymerization process proceeds with good monomer to polymer conversion efficiency. In particular, this invention relates to stable free radical-mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, multiblock copolymers, graft copolymers and the like, at enhanced rates of polymerization and enhanced monomer to polymer conversions.
US-A-4 581 429 to Solomon et al., issued April 8, 1986. discloses a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligo-meric homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R'R-N-0-X, where X is a free radical species capable of polymerizing unsaturated monomers. The reactions typically have low conversion rates. Specifically mentioned radical R'R-N-0« groups are derived from 1,1,3,3 tetraethylisoindoline, 1,1,3,3 tetrapropyiisoindoline. 2,2,6,6 tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine or di-t-butylamine. However, the suggested compounds do not fulfill all requirements. Particulariy the polymerization of acrylates does not proceed fast enough and/or the monomer to polymer conversion is not as high as desired.
The radical initiators, polymerization processes and resin products of the present invention have an additional glycidyl or carbonyl group, which can be used for further reactions. The resulting resins are useful in many applications.

The glycidyl or alkylcarbonyl group of the present initiators remains essentially unchanged during the radical polymerization reaction. Therefore the radical initiators of the present invention offer the possibility, after the radical polymerization is accomplished or stopped, to react the glycidyl group of the oligomers or polymers in a second step with nucleophiles such as alcohols, mercaptanes, amines, metal organic compounds or the like, thereby changing the properties of the oligomers or polymers.
The glycidyl group of the initiators can also be reacted in a first step for example by anionic polymerization in the presence of for example dicyandiamide, butyl-Lithium or other strong bases leading to oligomeric/polymeric radical initiators.
S. Kobatake et al, Macromolecules 1997, 30. 4238-4242 and in WO 97/36894 disclose the anionic polymerization of butadiene in the presence of compound (a) which contains a glycidyl group in a side chain. This compound acts as a terminating reagent for the anionic polymerization of butadiene.

The resulting macromolecule can be further used as a macroinitiator for radical polymerization and for preparing block copolymers containing a poylbutadiene segment. Typical copolymers which can be produced are acrylnitriie/butadiene/styrene (ABS) copolymers.
The present invention provides initiators for radical polymerization which contain the glycidyl or alkylcarbonyl group attached to the phenyl group. The initiators show a high reactivity, good rates of polymerization and good monomer to polymer conversions.

The remaining glycidyl or carbonyl group is highly reactive towards nucleophiles and can readily be transformed into other chemical groups if desired.
The compounds of the present invention are also useful as terminating agents in the anionic polymerization of for example butadiene as described in WO 97/36894. With the instant compounds termination of anionic polymerization of for example butadiene proceeds fast and complete.
Glycidyl or carbonyl functional alkoxyamines containing a tetramethyl-piperidine group and their use as functionaiized radical initiators/regulators have already been described in WO 99/46261. The instant compounds differ from those disclosed in WO 99/46261 in that they have a ketal structure in 4 position of the piperidine moiety. Such compounds and their use as polymerization initiators/regulators have neither been disclosed as specific compounds nor generically in the prior art.
It has now been found, that amongst those 2,2,6.6-tetraalkylpiperidines described in the prior art those are of particular value which are derivatives of 2,2,6.6 tetramethyl piperidine, 2,2 diethyl-6,6 dimethyl piperidine and of 2,6-diethyl-2,3,6-trimethyl piperidine which are substituted in the 4 position by two oxygen atoms forming an open chain or cyclic ketal structure.
The ketal stnjcture in 4 position ensures high thermal stability which is important for storage, particulariy at elevated temperatures. The ketal structure is themially significantly more • stable compared to the corresponding 4-oxo compound.
The compounds exhibit an unchanged initiating/regulating activity even after storage at elevated temperatures as for example used in conventional stability tests.
Another problem associated with nitroxyl or nitroxyl ether mediated free radical polymerization is the formation of a significant color of the resulting polymer. The compounds of the present invention which have a ketal structure in 4-position impart less color to the polymer compared to other prior art compounds of similar structure.

The steric hindrance introduced by the two diethyl groups instead of two methyl groups further leads to an optimized balance in temis of stability of the compounds, initiating activity and control of polymerization.
The particular substitution pattern in 2 and 6 position of the piperidine ring allows high monomer to polymer conversions in short times and low polydispersities which are generally below 2. High monomer to polymer conversions are even achieved with acrylates, such as ethyl- or butyl-acrylate. The temperature necessary to achieve high conversion in short times may be for example as low as 120°C.
The present invention provides compounds useful as initiators/regulators for controlled radical polymerization which in addition have a highly reactive functional group allowing polymer analogous reactions or anionic polymerization termination, which can be adjusted in their initiating/controlling efficiency by adjusting the steric hindrance at the nitrogen atom and which have an excellent storage stability and impart none or only little color to the final polymer.

R13 is phenyl or C1-C18alkyl; m is 1, 2 or 3; n is 1 or 2; if n is 1
Y and Y' are independently C1-C12alkyl. C3-C12alkenyl, C3-C12alkinyl, Cs-CecycloalkyI, phenyl,
naphthyl, Cy-Cgphenylalkyi; or
Y and Y' together fomi one of the bivalent groups -C(R0(R2)-CH(R3)-, CH(Ri)-CH2-
C(R2)(R3)-. -CH(R2)-CH2-C(R0(R3)-> -CH2-C(R0(R2)-CH(R3)-. o-phenylene, 1,2-
cyciohexyliden,

Z is Ci-Ci2alkylene;
the R12 are independently of each other H or CH3.
C1-C18alkyi can be linear or branched. Examples 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, heptadecyl or octadecyl.
Alkenyl having from 3 to 12 carbon atoms is a branched or unbranched radical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl.
Alkinyl having from 3 to 12 carbon atoms is a branched or unbranched radical, for example propinyl ( —CH2-C=ECH ). 2-butinyl, 3-butinyI, n-2-octinyl or n-2-dodecinyL
Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy. isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.
Cr-Cgphenylaikyi is for example benzyl, a-methyibenzyl. a,a-dimethylbenzyl or 2-phenylethyl, benzyl is preferred.
C1-C12alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene.
C5-C8cycloalkyI is for example cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl or cyclooctyl.
Examples of a monocarboxylic acid having up to 18 carbon atoms are formic acid, acetic acid, propionic acid, the isomers of valeric acid, methyl ethyl acetic acid, trimethyl acetic acid, capronic acid, lauric acid or stearic acid. Examples for unsaturated aliphatic acids are acrylic acid, methacrylic acid, crotonic acid, linolic acid and oleic acid.
Typical examples of cycloaliphatic carboxylic acids are cyclohexane carboxylic acid or cyclopentane carboxylic acid.

Examples of aromatic carboxylic acids are benzoic acid, salicylic acid or cinnamic acid.
Examples of dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebatic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid.

R1 is hydrogen, methyl or ethyl;
R2 and R3 are independently hydrogen, methyl ethyl, or C00-(CrCi2)alkyl; and
one of the R12 is hydrogen and the other is methyl.
Especially preferred is a compound of formula Ilia.
Specifically prefen-ed compounds are listed in Tables 1, 2 and 3.
Table 1
1.)2,6-Diethyl-4.4-dimethoxy-2,3,6-trimethyl-1-[1-(4-Oxiranyimethoxy-phenyl)-ethoxy]-piperidine

50 2,6-Diethyl-4,4-diisobutoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)ethoxy]-piperidine

6.) 2.6-Diethyl-2,3.6-trimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyI)-ethoxy^ piperidine

90 4,4-Bis-benzyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-ph piperidine

140 2-Butyl-7,9-diethyl-67.9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)ethoxyl}-1,4-dioxa-8-aza-spiro[4.5]decane

19.) Acetic acid 7,9-diethyl-67,9-trirnethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-yimethyl ester

20.) Octadecanoic acid 7,9-diethyl-6,7.9-trimethyl-8-I1-(4-Oxiranylmethoxy-phenyi)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester

240 2-Benzyloxymethyl-7,9-diethyl-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-ph 1.4-dioxa-8-aza-spiro[4.5]decane

25.) Octanedioic acid biS-{7.9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyl} ester

28.)7,9-Diethyl-2,2,67,9-pentamethyl-841-(4-oxiranylmethoxy-phenyl)-ethox aza-spiro[4.5]decane

29.) 7,9-Diethyi-2,3,6,7,9-pentamethyl-8-[1 -(4-oxiranylmethoxy-phenyI)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

330 8JO-Diethyl-7,8,10-trimethyl-9-[1-{4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa spiro[5.5]undecane

34.)8,10-Diethyl-3,37,8J0-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl}-ethoxy}-1,5-dioxa 9-a2a-spiro[5.5]undecane

38.)3-Butyl-3,8,10-triethyl-7,8J0-trimethyl-9-I1-(4-oxiranylmethoxy-ph dioxa-9-a2a-spiro[5.5]undecane

390 2.4-Diethyl-1,2.4-trimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy}-7,16-dioxa-3-aza dispiro[5.2.5.2]hexadec-11-ene

44.) 3-Benzyloxymethyl-8,10-diethyl-37,8.10-tetramethyl-9-[1-(4-oxiranyImethoxy ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

480 8,1O-Diethyl-3,7,8.10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-rthoxy}-1m5-dioxa-9-aza-spiro[5.5]undecane-3-carboxylic acid methyl ester

490 8,1O-Diethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-etho^^^ spiro[5.5]undecane-3.3-dicarboxylic acid diethyl ester

Table 2
10 2.2-Diethyl-4,,4-dimethoxy-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-pheny^ piperidine

6.) 2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy'1-[1-(4-ox!ranyimethoxy-phenyl)-ethoxy]-piperidine

11.) 7J-Diethyl-2,9,9-trimethyl-8-[1-(4-oxiranylnfiethoxy-phenyl)-ethoxy]1,4-dioxa-8-aza spiro[4.5]decane

150 77-Diethyl-9,9-iimethy!-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy}-1m4-dioxa-8-aza-spiro[4.5]decane

20.) Octadecanoic acid 77-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester

240 2-Ben2yloxymethyl-77-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-eth dioxa-8-aza-spiro[4.5]decane

25.) Octanedioic acid bis-{77-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl} ester

280 77-Diethyl'2,2,9,9-tetramethyl-841-(4-oxiranylmethoxy-phenyl)-eth spiro[4.5]decane

33.) 8,8-Diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

380 3-Butyl-3,8,8-triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phen 9-aza-spiro[5.5]undecane

43.)3-Cyclohexyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmeth ethoxy]-1,5-dioxa-9-a2a-spiro[5.5]undecane

47.) 1\6'-Bis-{3,8,8-triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-etho dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane

48.) 8,8-Diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-^ spiro[5.5]undecane-3-carboxylic acid methyl ester

51.) 2,2-Diethyl-4,4-dimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-a2a-spiro[5.6]dodec-9-ene

Table 3
1.) 4,4-Dimethoxy-2,2,6,6-tetramethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

5.) 4,4-Diisobutoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

nyI)-ethoxy]-piperidine 70 4,4-Bis-aIlyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidi^

9.) 4,4-Bis-ben2yloxy-2,2,6,6-tetramethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine

15.) 7,7,9,9-Tetramethyl-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane

20.) Octadecanoic acid 7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester

24.) 2-Ben2yloxymethyl-7,7,9,9-etramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,^ dioxa-8-a2a-spiro[4.5]decane

28.) 2,277,9,9-Hexamethyl-8-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-1,4-dioxa-^^^ spiro[4.5]decane

290 2.37.7,9,9-Hexamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-diox^^^ spiro[4.5]decane

38.) 3-Butyl-3-ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-pheny!)-ethoxy^ 9-aza-spiro[5.5]undecane

43.) 3-Cyclohexyloxymethyl-3,8.8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy-pheny^ ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane

480 3,8,810,1O-Pentamethyl-9-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-1,5-diox spiro[5.5]undecane-3-carboxylic acid methyl ester

Particularly preferred are the following compounds: 4,4-Dibutoxy-2,6-diethyl-2,3,6-trirnethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-p^

7.9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-^ spiro[4.5]decane

77-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]decane

7,7,9.9-Tetramethy!-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro[4.5)decane

A further subject of the invention is a polymerizable composition, comprising
a) at least one ethylenically unsaturated monomer or oligomer, and
b) a compound of formula la, lla or Ilia

Ri3 is phenyl or CrCiealkyI; m is 1, 2 or 3; n is 1 or 2; if n is 1
Y and Y* are independently C1-C12alkyl, C3-C12alkenyl, C3-C12alkinyl, Cs-CBcycloalkyI, phenyl,
naphthyl, Cr-Cophenylalkyl; or
Y and Y' together form one of the bivalent groups -C(Ri)(R2)-CH(R3)-, CH(Ri)-CH2-
C(R2)(R3)-. -CH(R2)-CH2-C(Ri)(R3)-, -CH2-C(Ri)(R2)-CH(R3h o-phenylene, 1,2-
cyclohexyliden,

Definitions and preferences have already been given above for the compounds. They apply also for the composition.
The monomers suitable for use in the present invention may be water-soluble or water-insoluble. Water soluble monomers contain typically a salt of a carboxylic acid group. Water insoluble monomers are typically free of acid and phenolic groups. Typical metal atoms are Na, K or Li.
Typical monoethylenically unsaturated monomers free of carboxylic acid and phenolic groups which are suitable for this invention include the alkyl esters of acrylic or methacrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate; the hydroxyalkyi esters of acrylic or methacrylic acids, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide, methacrylamide, N-tertiary butylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide; acrylonitrile, methacrylo-nitrile, allyl alcohol, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,

phosphoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, vinyl acetate, conjugated dienes such as butadiene or isoprene, styrene, styrenesulfonic acid salts, vinylsulfonic acid salts and 2-acrylamidO-2-methylpropane-sulfonic acid salts and acryloil chloride.
Preferred ethylenically unsaturated monomers or oligomers are selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.
Particularly preferred ethylenically unsaturated monomers are styrene. a-methyl styrene, p-methyl styrene, butadiene, methylacrylate, ethylacrylate, propyjacrylate, n-butyl acrylate, tert.-butyl acrylate and acrylnitril.
In a most preferred composition the ethylenically unsaturated monomer is styrene.
Preferred acrylates are methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butyiacrylate, hydroxyethylacrylate. hydroxypropylacrylate, dimethylaminoethyiacryjate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate. butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate. glycidyl(meth)acryiates, acrylonitrile, acrylamide or methacrylamide.
Examples for C8-C16 ethylenically unsaturated phenolics, which may also be used as comonomers include 4-hydroxy styrene, 4-hydroxy-a-methyl styrene, and 2,6-ditert, butyl, 4-vinyl phenol.
Another class of carboxylic acid monomers suitable for use as comonomers in this invention are the alkali metal and ammonium salts of C4-C6-ethylenically unsaturated dicarboxylic acids. Suitable examples include maleic acid, maleic anhydride, itaconic acid, mesaconic acid, fumaric acid and citraconic acid. Maleic anhydride (and itaconic acid are) is the preferred monoethylenically unsaturated dicarboxylic acid monomer(s).
The acid monomers suitable for use in this invention are in the form of the alkali metal salts or ammonium salts of the acid.

The polymerizable composition of the present invention may additionally comprise a solvent selected from the group consisting of water, alcohols, esters, ethers, ketones, amides, sulfoxides, hydrocarbons and halogenated hydrocarbons.
The invention also relates to a free radical polymerization process and polymers obtained thereby, which process overcomes many of the problems and disadvantages of the afore mentioned prior art processes.
Preferably the initiator compound is present in an amount of from 0.01 mol-% to 20 mol-% , more preferably in an amount of from 0.01 mol-% to 10 mol-% and most preferred in an amount of from 0.05 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 of formula la, lla or Ilia under reaction conditions capable of effecting scission of the 0-C bond to form two

The process may be carried out in the presence of 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.
Prefen-ed 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 prefen-ably 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), halogenated 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 homogeneous single phase throughout the monomer 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, pyn-olidines, N-alkyI pyn-olidinones, 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 cellosolve, 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.
When monomer mixtures or monomer/oligomer mixtures are used, the calculation of mol-% is based on an average molecular weight of the mixture.

Hydrophilic monomers, polymers and copolymers of the present invention can be separated from one another or from the polymerization reaction mixture by, for example, changing the pH of the reaction media and by other well known conventional separation techniques.
The polymerization temperature may range from about 50°C to about 180°C, preferably from about 80°C to about 150°C. At temperatures above about 180°G, the controlled conversion of the monomer into polymer decreases, and uncertain and undesirable by-products like thermally initiated polymer are formed or destruction of the polymerization regulator may occur. Frequently, these by-products discolor the polymer mixture and a purification step may be required to remove them, or they may be intractable.
Therefore high reactivity of the present initiators which are already active at relatively low temperatures leads to short reaction times. The resulting polymers are usually colouriess and they can be used in most cases without any further purification step. This is an important advantage when industrial scale-up is considered.
After the polymerizing step is complete, the formed (co)polymer obtained is isolated. The isolating step of the present process is conducted by known procedures, e.g. by distilling off the unreacted monomer or by precipitation in a suitable nonsolvent, filtering the precipitated polymer followed by washing and drying the polymer.
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.
The (co)polymers of the present invention may have a number average molecular weight from 1 000 to 400 000 g/mol, preferably from 2 000 to 250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mo1. When produced in bulk, the number average molecular weight may be up to 500 000 (with the same minimum weights as mentioned above). The number average molecular weight may be determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC), matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) or, if the initiator carries a group which can be easily distinguished from the monomer(s), by NMR spectroscopy or other conventional methods.
Thus, the present invention also encompasses in the synthesis novel block, multi-block, star, gradient, random, hyperbranched and dendritic copolymers, as welf as graft or copolymers.

The polymers prepared by the present invention are useful for example in following applications:
adhesives. detergents, dispersants, emulsifiers, surfactants, defoamers, adhesion promoters, corrosion inhibitors, viscosity improvers, lubricants, rheology modifiers, impact modifiers, thickeners, crosslinkers, paper treatment, water treatment, electronic materials, paints, coatings, photography, ink materials, imaging materials, superabsorbants, cosmetics, hair products, preservatives, 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 will. Furthermore, the polymer product retains the functional alkoxyamine group allowing a continuation of the polymerization in a living matter. Thus, in one embodiment of this invention, once the first monomer is consumed in the initial polymerizing step a second monomer 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 order. One is not necessarily restricted to preparing block copolymers where the sequential polymerizing 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 possible to prepare a multi-block copolymer in which a polyacrylonitrile or a poly(meth)-acrylate block is prepared first, then a styrene or butadiene block is attached thereto, and so on.
Furthermore, there is no linking group required for joining the different blocks of the present block copolymer. One can simply add successive monomers to form successive blocks.
A plurality of specifically designed polymers and copolymers are accessible by the present invention, such as star and graft (co)polymers as described, inter alia, by C. J. Hawker in Angew. Chemie, 1995, 107, pages 1623-1627, dendrimers as described by K. Matyaszewski et al. in Macromolecules 1996, Vol 29, No. 12, pages 4167-4171, graft (co)polymers as described by C. J. Hawker et al. in Macromol. Chem. Phys. 198, 155-166(1997), random copolymers as described by C. J. Hawker in Macromolecules 1996, 29, 2686-2688, or

Also subject of the invention is the use of a compound of formula la, ila or Ilia for terminating the anionic polymerization of a diene or vinyl monomer.
When the compounds are used for such termination reactions they are usually used in an -equimolar amount or in excess to the initiating base, such as for example sec. butyl-litium.
The preparation of the compounds of the present invention is carried out according to known reaction steps. A general method for the preparation of the compounds of formula la, Ila, and Ilia starts from the 4-oxo compounds Xa or Xla which are described in GB 2335190 or from Xlla which is a known compound described for example in DE 2352127.

The compounds of formula Xb, Xlb and Xllb are oxidized according to standard procedures to the corresponding nitroxides of formula Xc, Xlc and Xllc, as for example described in GB 2335190 or WO 99/46261.

formula la, lla or Ilia.
This coupling reaction is also descriebed for example in GB 2335190 or in WO 99/46261. Preferably the coupling reaction is carried out in the presence of a Cu(ll) salt according to the method described in International Application No. PCT/EP01/05668.

These compounds are novel and consequently are also subject of the present invention. The above given definitions and preferences apply also for the compounds of formula Xd, Xld and Xlld.

The compounds of formula Xd, Xld and Xlld can be reacted with epichlorohydrine and compounds according to formula la, lla or Ilia are obtained.
The following examples illustrate the invention.
Preparation of an intermediate according to formula Xlld.

A mixture of 25,6 g 3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (prepared according to EP 574666A1) and 82,1 g acetic acid 4-ethyl-phenyl ester are heated to 50°C with stirring and 0,68 ml of an ethanolic solution containing 0,13 g copper(ll)chloride is added. The temperature, is raised to 65°C and 19,4 g of an aqueous solution of butylhydroperoxide in water (70%) are dropwise added. The reaction mixture is allowed to further react for 22h at 65°- 70°C and subsequently cooled to room temperature. Excess tert.-butylhydroperoxide is removed by dropwise adding 4m! of an aqueous sodium pyrosulfite solution (20%). To the reaction mixture 5Dml acetic acid ethylester are added and the organic and aqueous phase are separated. The organic phase is washed with a saturated NaCI solution. After drying with sodium sulfate and evaporation of the solvent an oil is obtained, from which excess acetic acid 4-ethyl-phenyl ester is removed by distillation (100°C/0,025 mbar). The residue is dissolved in methanol/hexane (4/1 by volume) on heating to refux. After cooling to 0°C the precipitate is filtered off. After recrystalization from acetone white crystals are obtained having a melting point of 124 -125°C.

A mixture of 8 g acetic acid 4-[1-(3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-a2a-spiro[5.5]undec-9-yloxy)-ethyl]-phenyl ester and 3,9 g potassium carbonate in 60 ml methanol is stirred for one hour at room temperature. The mixture is cooled to O°C and neutralized by adding 60 ml of 0.5 M hydrochloric acid. The white suspension is diluted with water (60 ml) and filtered through a buchner funnel. The residue is washed with water and dried in a vacuum oven at SOX. A white solid having a melting point of 133 - 134°C is obtained.

A mixture of 50 g 7,7,9.9-tetramethyl-1,4-dioxa-8-a2a-spiro[4.5]decan-8-oxyl (prepared according to EP 574666A1) and 124,75 g 2-(4-ethyl-phenoxymethyl)-oxiran are heated to 60** C with stirring and a solution of 0,32 g copper(ll)chloride in 1,6 ml ethanol is added. 45 g of an aqueous solution of butylhydroperoxide in water (70%) is dropwise added. The reaction mixture is allowed to further react for 16h at 60° C and subsequently cooled to room temperature. Excess tert.-butylhydroperoxide is removed by dropwise adding 15ml of an aqueous sodium pyrosulfite solution. To the reaction mixture 100ml acetic acid ethylester are added and the organic and aqueous phase are separated. The organic phase is washed twice with 200 ml of a saturated NaCI solution. After drying with sodium sulfate and evaporation of the solvent an oil is obtained, from which excess 2-(4-ethyl-phenoxymethyl)-oxiran is removed by distillation (100°C/0,005 mbar). The residue is dissolved in hexane filtered over aluminium oxide and the solvent is again evaporated. After recrystalization from hexane white crystals are obtained having a melting point of 73.5-74.2*' C.

The title compound is prepared in analogy to example A1 from 3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (prepared according to EP 574666A1). White crystals are obtained.
Elemental analysis: calculated: 69.25% C; 9,07% H; 3,23% N; found:68,86% C; 9,05% H; 3.18% N.

A mixture of 50 g 3,3,8,8,10,10-hexamethyl-l.5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl (CAS 98254-32-1) and 41 g (4-Ethyl-phenyl)-phenyl-methanone (preparation by Friedel-Crafts acylation of 4-ethylben2ene with benzoylchloride) is heated to 60'C and a solution of 0,26 g copper(ll)chloride in 1,3 ml ethanol is added. 53,7 g of a 70% aqueous solution of tert-butylhydroperoxide in water are added dropwise. The reaction mixture is allowed to further react for 28 h and subsequently cooled to room temperature. Excess tert-butylhydroperoxide

is then removed by dropwise adding an aqueous solution of sodium pyrosulfite. To the reaction mixture 100 ml of ethyl acetate are added and the organic phase is separeted from the aqueous phase. The organic phase is washed twice with water (200 ml) and the solvent evaporated. The residue is purified chromatographicaliy on silica gel with hexane/ethyl acetate (7:3 by volume) as the eluente. After recrystaliization from pentane/ethanol (5:3 by volume) white crystals of a compound of formula

are obtained having a melting range of 104 - 117°C.
'H-NMR (300 MHz; 5 in ppm; CDCI3): 0,7 (s broad, 3 H); 0,94 (s broad, 6 H); 1,18 (s broad. 3 H); 1.33 (s broad, 6 H); 1.51.1.53 (d, 3 H); 1,4-1,65 (m. 2 H); 2-2.25 (m. 2 H); 3.46 (s broad, 4 H); 4,84-4.91 (q. 1 H); 7.4-7,9 (aromatic H. 9 H).
Example A19: 8.8-Diethvl-3.3.10,10'tetramethvl-9'f1-(4-oxiranvlmethQxv-phenvl)-ethoxv1-1.5-dioxa-9-aza-spirof5.51undecane
To a stirred mixture of 25.6 g 8,8-diethyl-3.3,10,10-tetramethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl and 80,2 g 2-(4-ethyl-phenoxymethyl)-oxirane at 50°C is added a solution of 0,12 g copper(ll)chloride in 0,6 ml ethanol. The temperature of the reaction mixture is increased to 70°C and 11.6 g of a 70% aqueous solution of tert-butylhydroperoxide in water are added dropwise. The reaction mixture is allowed to further react for 6 h at 70°C and subsequently cooled to room temperature. Excess tert-butylhydroperoxide is removed by dropwise adding an aqueous solution of sodium pyrosulfite (2 ml). To the reaction mixture 50 ml of ethyl acetate and 50 ml 10% aqueous solution of sodium chloride are added. The mixture is filtered through celite and the organic phase is separeted. The organic phase is washed three times with 10% aqueous solution of sodium chloride (100 ml) and dried over sodium sulfate. After evaporation of the solvent an oil is obtained, from which excess 2-(4-ethyl-phenoxymethyl)-oxirane is removed by distillation (80°C, 0,025 mbar). A highly viscous residue is obtained which crystallises on standing at room temperature. After recrystaliization twice from methanol white crystals of

To a stirred mixture of 59,7 g 8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecan-9-oxyl and 178,2 g 2-(4-ethyi-phenoxymethyl)-oxirane a solution of 0,27 g copper(ll)chloride in 1,35 ml ethanol is added at about 60°C. Then 38.7 g of a 70% aqueous

solution of tert-butylhydroperoxide in water are added dropwise. An exothermic reaction started and the temperature is kept at 70°C. The reaction mixture is allowed to further react ■ for 24 h at 70°C and subsequently cooled to room temperature. The reaction mixture is diluted with 100 ml of ethyl acetate. Excess tert-butylhydroperoxide is removed by dropwise adding an aqueous solution of sodium pyrosuifite (70 ml) below 20°C. The organic phase is separeted, washed twice with 10% aqueous solution of sodium chloride (100 ml) and dried over sodium sulfate. After evaporation of the solvent an oil is obtained, from which excess Z-* (4-ethyl-phenoxymethyl)-oxirane is removed by distillation (80°C, 0,025 mbar). A highly viscous resin

degassed in three consecutive freeze-thaw-cycles and then purged with argon. The stirred solution is then immersed in an oil bath and polymerized at the given temperature for 6 hours. After polymerization, residual monomer is removed under vacuum at 60°C and the polymer is dried at 60°C in vacuo until constant weight is achieved. Molecular weight and molecular weight distributions are determined by size exclusion chromatography (SEC) on a HP 1090 liquid chromatograph (software: winGPC / Polymer Standard Services, Mainz, Germany) using THF as eluent and a column combination calibrated with narrow polystyrene standards (Polymer Laboratories). The results are given in Table 1.

Polymerization with n-BuA
Example B7
n-Butylacrylate is destilled under reduced pressure prior to use. In a dry, argon-purged Schlenk tube, the amounts of nitroxyl ether given in Table A are dissolved in 62.5 ml n-butylacrylate. The solution is degassed in three consecutive freeze-thaw-cycles and then purged with argon. The stirred solution is then immersed in an oil bath and polymerized at

130°C for 6 hours. After polymerization, residual monomer is removed under vacuum at 30°C and the polymer is dried at 30°C in vacuum until constant weight is achieved.
Molecular weight and molecular weight distributions are determined by size exclusion chromatography (SEC) on a HP 1090 liquid chromatograph (software: winGPC / Polymer Standard Services, Mainz, Germany) using THF as eluent and a column combination calibrated with narrow polystyrene standards (Polymer Laboratories). The results are giva§ in Table 7.

Example B8: Anionic polymerization and termination of isoprene with the compound of example A2
To 10.2 g (0.15 mol) isoprene dissolved in 50 ml dry toluene in a dried ampule with teflon valve equipped with a magnetic stir bar are added in a dry argon atmosphere 3,34 x 10'^ mol sec.-butyllithium (1.3 mol/L solution in cyclohexane, Fluka) and stirred for 18 hours at room temperature to allow polymerization. Subsequently a sample of the resulting prepolymer is drawn via syringe, dried at room temperature in vacuo and submitted to GPC. To the residual, slightly yellow polyisoprene solution is slowly added a calculated amount of the compound of example A2 (1.2 and 1.5 fold molar excess with respect to the initial molar amount of sec.-butyllithium used) (dissolved in toluene and degassed) via syringe. The mixture is allowed to react for another 6 hours at room temperature. Subsequently the termination reaction is quenched adding a few ml of degassed methanol. Volatiles are removed in vacuo and the resulting polyisoprene is obtained as a slight yellow rubber after

drying at room temperature in vacuo until constant weight is achieved. Molecular weights are determined by GPC on a HP 1090 equipped with a Rl and DAAD (set at 254 nm) detector with THF as efuent (1 ml/min), using PS standards for calibration.

R13 is phenyl or C1-C18alkyl; m is 1, 2 or 3; n is 1 or 2; if n is 1
Y and Y' are independently C1-C12alkyl, C3-C12alkeny!, C3-C12alkinyl, Cs-Cecycloalkyl, phenyl, naphthyl, Cr-CsphenylalkyI; or
Y and r together form one of the bivalent groups -C(Ri)(R2)-CH(R3)-, CH(Ri)-CH2-C(R2)(R3)-, -CH(R2)-CH2-C(Ri)(R3)-. -CH2-C(R1)(R2)-CH(R3)-, o-phenylene, 1,2-cyclohexyliden,

R4 is hydrogen. C1-C12alkyl, benzyl, or a monovalent acyl residue derived from an aliphatic,
cycloaliphatic or aromatic monocarboxylic acid having up to 18 carbon atoms;
if n is 2
Y and Y' together form one of the tetravalent groups

Y and Y' together form one of the bivalent groups -C(R1)(R2)-CH(R3)-. CH(R1)-CH2-
C(R2)(R3K -CH(R2)-CH2-C(Ri)(R3)-. -CH2-C(R1)(R2^CH(R3)^ -CH2-CH=CH-CH2- or
wherein
Ri is hydrogen, CrCi2alkyl. C00-(Ci-Ci2)alkyl or CH2OR4;
R2 and R3 are independently hydrogen, methyl ethyl, or C00-(C1-C12)alkyl;
R4 is hydrogen, C1-C12alkyl, benzyl, or a monovalent acyl residue derived from an aliphatic,
cycloaliphatic or aromatic monocarboxylic acid having up to 12 carbon atoms and
one of the R12 is hydrogen and the other is methyl.

m is1; n is 1 ;
Y and Y' together form one of the bivalent groups -CH2-C(Ri)(R2)-CH(R3)- wherein
Ri is hydrogen, methyl or ethyl;
R2 and R3 are independently hydrogen, methyl ethyl, or C00-(CrCi2)alkyl; and one of the R12 is hydrogen and the other is methyl.
5. A compound according to claim 1 which is of formula Ilia.
6. A compound according to claim 1 of formula la, lla or Ilia which is
1.) 2,6-Diethyl-4,4-dimethoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
2.)4,4-Diethoxy-2,6-diethyl-2.3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
3.)2,6-Diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxyH,4-dipropoxy-
piperidine
4.)4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
5.)2,6-Diethyl-4,4-diisobutoxy-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine

6.) 2,6-Diethyl-2,3.6-trimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy}-
piperidine
70 4,4-Bis-allyloxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
8.) 4,4-Bis-cyclohexyloxy-2,5-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-eth
piperidine
90 4,4-Bis-benzyloxy-2.6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
10.) 7,9-Diethyl-6J.9-trJmethyl-8-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane
11.) 7,9-DiethyI-2,6,7,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane
12.) 2J,9-Triethyi-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza
spiro[4.5]decane
13.) 7,9-Diethyl-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyl-1,4-dioxa-8-
a2a-spiro[4.5]decane
14.) 2-Butyl-7,9-diethyl-6J,94rimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-di
aza-spiro[4.5]decane
15.)7,9-Diethyl-6J,9-trimethyi-2-octyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-
a2a-spiro[4.5]decane
16.) 2-Decyi-7.9-diethyl-6J,9-trimethyl-8-[1-(4-Oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-
a2a-spiro[4.5]decane
17.) 2-Dodecyl-7,9-diethyl-6J,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4
8-a2a-spiro[4.5]decane
18.){7,9-Diethyl-67,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza
spiro[4.5]dec-2-yl}-melhanol
19.) Acetic acid 7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranytmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl ester
20.) Octadecanoic acid 7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
1.4-dioxa-8-aza-spiro[4,5]dec-2-y!methyl ester
21.) Benzoic acid 7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-aza-spiro[4.5]dec-2-ylmethyl ester
22.) 7,9-Diethyl-2-nriethoxymethyl-6,7,9-trimethyl-8-I1-(4-oxiranylnriethoxy-phenyl)-ethoxy]-
1,4-dioxa-8-aza-spiro[4.5]decane

230 2-Cyclohexyloxymethyl-7.9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phen
ethoxy]-1,4-dioxa-8-aza-spiro[4.5]decane
24.) 2-Benzyloxymethyl-7,9-diethy!-6,7,9-trimethyl-8-1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
1,4-dioxa-8-a2a-spiro[4.5]decane
25.) Octanedioic acid bis-{7,9-diethyl-6.7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-
ethoxy]-1,4-dioxa-8-a2a-spiro[4.5]deC-2-ylmethyl} ester
26.) Terephthalic acid bis-{7,9-diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-
ethoxy]-1,4-dioxa-8-aza-spiro[4.5]dec-2-ylmethyi} ester
27.) 1\4*-Bis-{7,9-diethyl-67.9-trimethyl-8-(1-(4-oxiranylmethoxy-phenyl)-ethoxy)-1,^
8-a2a-spiro[4 28.)7.9-Diethyl-2,2,6J,9-pentamethyl-841-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa^^^
aza-spiro[4.5]decane
290 7,9-Diethyi-2,3,67,9-pentamethyl-8-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-1,4-dioxa-8--
aza-spiro[4.5]decane
30.) 4,4-(o-Phenylendioxy)-2,6-diethyl-2,3,6-trimethyl-1-[V-(4'-oxiranylmethoxy-phenyl)-
ethoxyj-piperidine
31.)4.4-(1\2'-cyclohexylendioxy)-2,6-diethyl-2,3,6-trimethyl-1-[r'-(4'-oxiranylmethoxy-
phenyl)-ethoxy]-piperidine
320 7.9-Diethyl-6,7,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane-2,3-dicarboxylic acid dimethyl ester
33.) 8,10-Diethyl-7,8J0-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane 34.)8,10-Diethyl-3,3,7,8,10-pentamethyl-9-1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-
9-aza-spiro[5.5]undecane 35.)3,8J0-Triethyl-3,7,8,10-tetramethyl-9-[1-(4-oxirany!methoxy-phenyi)-ethoxy]-1,5'di
9-aza-spiro[5.5]undecane
36.) 3.3,8J0-Tetraethyl-7,8J0-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-
9-aza-Spiro[5.5]undecane
37.) 8JO-Diethyl-3J,8JO-tetramethyl-9-[1-(4-oxiranylrnethoxy-phenyi)-ethoxy]-3-propyl-1,5-
dioxa-9-aza-spiro[5.5]undecane
380 3-Butyl-3,8,10-triethyl-7,8,10-trirnethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5
diGxa-9-aza-spiro[5.5]undecane 39.)2,4-Diethyl-1,2,44rinriethyt-3-[1-{4-oxiranylrneihoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-
dispiro[5.2.5.2]hexadec-11-ene

40.){8,10-Diethyl-3,7,8.10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]1,5-dioxa-9-
aza-spiro[5.5]undec*3-yl}-methanol
410{3.8,10-Tnethyl-7.8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethyoxy]-1m5-dioxa-9-
aza-spiro[5.5]undec-3-yl}-methanol
42.) 8.10-Diethyl-3-methoxymethyl-3J,8J0-tetramethyl-9-[1-(4-oxiranyimethoxy-phenyl)-
ethoxy]-1,5-dioxa-9-aza-spiro[5,5]undecane
43.) 3-CyclohexyIoxymethyl-8,10-diethyi-3,7,8J0-tetramethyl-9-[1-(4-oxiranyImethoxy-
phenyl)-ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane
44.)3-Benzyloxymethyl-8J0-diethyl-3J,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl
ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane
45.) Acetic acid 8,10-diethyl-3J,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl ester
46.) Octanedioic acid bis-{8,10-diethyl-3J,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-
ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl} ester
47.) 1\6'-Bis-^3.8J0-triethyl-7,8J0-trimethyl-9-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1.5-
dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane
48.)8J0-DJethyl-37,8J0-tetrarnethyl-9-[1-(4-oxiranylmethQxy-phenyl)-ethoxy]-1,5-dioxa-9-
aza-spiro[5.5]undecane-3-carboxy!ic acid methyl ester
49.) 8J0-Diethyl-7,8J0-trirnethyl-9-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane-3,3-dicarboxylic acid diethyl ester
50.)33-Bis^8,10-diethyl-7,8,104rimethyl-9-[1-(4--oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa--
9-aza}-spiro[5.5]undecane 51.)2,4-Diethyl-1,2,4-trimethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3'aza-
spiro[5.6]dodec-9-ene
52.) 2,2-Diethyi-4,4-dimethoxy-6.6-dimethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
530 4,4-Diethoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine
54.) 2,2-Diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-4,4-dipropoxy-
piperidine 55.)4,4-Dibutoxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine
56.) 2,2-D!ethyl-4,4-diisobutoxy-6,6-dimethyl-1 -[1 -(4-Oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
57.)2,2-Diethyl-6,6-dimethyl-4,4-bis-octyloxy-1-[1-(4-oxiranylmethoxy-phenyl)-eihoxy]-
piperidine

58.)4,4-Bis-allyloxy-2,2-diethyl-6,6-dimethyl-1-[1-{4-oxiranylmethoxy-phenyI)-etho
piperidine
59.) 4,4-Bis-cyclohexyloxy-2,2-diethyl-6,6-dimethy!-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
60.)4,4-Bis-benzyloxy-2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-pheny!)-ethoxy]-
piperidine
61.) 77-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyi)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
62.) 7,7-Diethy!-'2,9,9-trimethy!-8-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane
63.) 2.7 J-Triethyl-9,9-dimethyl-8-[1 -(4-oxiranylmethoxy-phenyI)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
64.)7J-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyI)-ethoxy]-2-pra^
a2a-spiro[4.5]decane
650 2-Butyl-77-diethy(-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1^
a2a-spiro[4.5]decane
66.) 77-Dtethyl-9,9-dimethyl-2-octyl-8-[1-(4-oxirany!methoxy-phenyl)-ethoxy]-1,4-d
aza-spiro[4.5]decane
67.)2-Decyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-
a2a-spiro[4.5]decane
680 2-Dodecy)-77-diethyl-9,9-dimethyl-841-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-diox
a2a-spiro[4.5]decane
690{77-Diethyl'9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]dec-2-y(}-methanol
70.) Acetic acid 7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-
8-aza-spiro[4.5]dec-2-ylmethyl ester
71.) Octadecanoic acid 7,7-diethy(-9.9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.4-
dioxa-8-a2a-spiro[4.5]dec-2-ylmethyI ester
72.) Ben2oic acid 7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-
8-a2a-spiro[4.5]dec-2-ylniethyl ester
73.) 77-Diethyl-2-methoxymethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-a2a-spiro[4.5]decane
74.) 2-Cyclohexyloxymethyl-77-diethyl-9,9-d(methyl-8-[1-(4-oxiranylrnethoxy-phenyl)-
ethoxy]-1,4-d!oxa-8-a2a-spiro[4.5]decane

75.) 2-Benzyloxymethyl-7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-a2a-spiro[4.5]decane
76.) Octanedioic acid bis-{7,7-diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl} ester
77.) Terephthalic acid bis-{7,7-diethyl-9,9-dimetlnyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
1,4-dioxa-8-a2a-spiro[4.5]dec-2-ylmethyl} ester
78.) 1\4'-Bis-{7,7-diethyl-9,9-diniethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-
aza-spiro[4,5]dec-2-ylmethyl}-oxybutane
79.) 7,7-Diethyl-2,2.9,9-tetramethyl-8-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
80.) 7J-Diethyl-2,3,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
81.)4,4-(o-Phenylendioxy)-2,2-diethyl-6,6-dimethyl-1-[1'-(4'-oxiranylmethoxy-phenyl)-
ethoxy]-piperidine
82.)4,4-(1\2'-cydohexyiendioxy)-2,2-diethyl-6,6-dimethyl-1-[1'(4'-oxiranylmethoxy-ph
ethoxy]-piperidine
83.) 7,7-Diethyl-9,9-dimethyl-8-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane-2,3-dicarboxylic acid dimethyl ester
84.) 8,8-Diethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-9-aza-
spJro[5.5]undecane
85.) 8,8-Diethyl-3,3J0J0-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-
aza-spiro[5.5]undecane 86.)3,8,8-Triethyl-3.10J0-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dio^^^
aza-spiro[5.5]undecane 87.)3,3,8,8-Tetraethyi-10,10-dimethyl-9-[1-(4-oxiranylrriethoxy-phenyl)-ethoxy]-1,5-dicxa-9- •
aza-spiro[5.5]undecane 88.)8,8-Diethyl-3,10,10-trimethyl-941-(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-^
dioxa-9-aza-spiro[5.5]undecane 89.)3-Butyl-3,8,8-triethyl-10J0-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethaxy]-1.5-dioxa-
9-a2a-spiro[5.5]undecane 90.)2.2-Diethyl,4-dimethyl-3-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-
dispiro[5.2.5.2]hexadec-11-ene
910{8,8-Diethyl-3,10,10-trimethyl'-[1-(4-oxiranylmethoxy-phenyl)-ethGxy]-1,5-d^
spiro[5.5]undec-3-yl}-methanol

92.) {3,8,8-Triethyl-10.10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-^
spiro[5.5]undec-3-yl-methanol
93.) 8,8-Diethyl-3-methoxymethyl-3,10,10-trimethy!-9-[1-(4-oxiranylmethoxy-phenyl)-^^^
1,5-dioxa-9-aza-spiro[5.5]undecane
94.) 3-Cyclohexyloxymethyl-8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranyImethoxy-phe
ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane
95.) 3-Benzyloxymethyl-8,8-diethyl-3,10,10-rirnethyl-9-[1-(4-oxiranylmethoxy-phenyl)-
ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undecane
96.) Acetic acid 8,8-diethyl-3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-
dioxa-9-aza-spiro[5.5]undec-3-yimethyl ester
97.) Octanedioic acid bis-{8,8-diethyl-3,10,10-trimethyl-9-[1-(4-Gxiranylmethoxy-phenyl)-
ethoxy]-1,5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl} ester
98.) 1\6'-Bis-{3,8,8-triethyl-10,10-dimethyl-9-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-
dioxa-9-aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane
99.) 8,8-Diethyl-3,10J0-trimethyl-941-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane-3-carboxylic acid methyl ester
100.) 8,8-D!ethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane-3,3-dicarboxylic acid diethyl ester
101.)3,3-Bis-{8.8-diethyl-10,10-dimethyl-9-[1-(4--oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-
9-aza}-spiro[5.5]undecane
102.)2,2-Diethyl-4.4-dimethyl-3-[1-(4-oxiranylniethoxy-phenyl)-ethoxy]-7J2-dioxa-3-aza^
spiro[5.6]dodec-9-ene
103.)4,4-Dimethoxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine
104.) 4,4-Diethoxy-2,2,6,6-tetramethyl-1-[1-(4-OXiranylmethoxy-phenyI)-ethoxy]-piperidine
105.) 2,2,6,6-Tetramethy!-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxyH,4-dipropoxy-piperidine
106.)4,4-Dibutoxy-2,2,6,6-tetramethyI-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine
107.)4,4-Diisobutoxy-2.2,6,6-tetramethy!-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidine
108.) 2,2,6,6-Tetramethyl-4,4-bis-octyloxy-1-[1-(4-oxirany!methoxy-phenyl)-ethoxy]-
piperidine
109.)4,4-Bis-allyloxy-2,2,6,6-tetramethyi-1-[1-(4-oxiranylmethoxy--phenyl)-ethoxy]-piperidine
110.) 4.4-Bis-cyclohexyloxy-2,2,6,6-tetramethyl-1 -[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-
piperidine
111.)4,4-Bis-benzyloxy-2,2,6,6-tetramethyl-1-[1-(4-oxiranyimethoxy-phenyl)-ethoxy]-
pipendine

112.) 77,9,9-Tetramethyl-8-I1--(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
113.) 2,7,7,9,9-Pentamethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.4-dioxa-8-a2a-
spiro[4.5]decane
114.) 2-Ethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
115.) 7.7,9,9-Tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-2-propyi-1,4-dioxa-8-aza-
spiro[4.5]decane
116.) 2-Butyl-7J,9,9-tetramethyl-8-[1-(4'Oxiranylrnethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane
117.)7,7.9,9-Tetramettyl-2-octyl-841-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-d
spiro[4.5]decane
118.) 2-Decyi-77,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane
119.) 2-Dodecyl-7,7,9,9-tetramethyl-8-[1 -(4-oxiranylmethoxy-phenyI)-ethoxy]-1,4-dioxa-8-
aza- spiro[4.5]decane
120.){7J,9,9-Tetramethyl-8-[1--(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]dec-2-yl}-methanol
121) Acetic acid 7J,9,9-tetramethyl-8-[1-(4-oxJranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-
aza-spiro[4.5]dec-2-ylmethyl ester
122.) Octadecanoic acid 7,7.9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-aza-spiro[4.5]dec-2-ylmethyI ester
123.) Benzoic acid 7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-
aza-spiro[4.5]dec-2-ylmethyl ester
124.) 2-Methoxyrnethyl-7J,9,9-tetrarnethyl-8--[1-{4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-aza-spiro[4.5]decane 125.)2-Cyclohexyloxyrnethyl-7,7,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-
1,4-dioxa-8-aza-spiro[4.5]decane
126.) 2-Benzyloxymethyl-7,7,9,9--tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-aza-spiro[4.5]decane
127.) Octanedioic acid bis-{7,7,9,9-tetramethyl-8-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dioxa-8-aza-spiro[4.5]dec-2-y!methyl} ester
128.) Terephthaiic acid bis-{7,7,9.9-tetramethyl-8-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-
dJoxa-8-aza-spiro[4.5]dec-2-ylmethyi} ester

129.) 1'4'-Bis-(77,9,9-tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa"^^^
spiro[4.5]dec-2-yimethyl}-oxybutane
130.) 2,27,7,9.9-Hexamethyl-8-[1-(4-oxiranylrnethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane
131.) 2,3,7,7,9,9-Hexamethyl-8-[1-(4--oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa"8-a2a-
spiro[4.5]decane
132.)4,4-(o-Phenylendioxy)-2,2,6,6-tetramethyl-1-[1'-(4'-oxiranylmethoxy-phenyl)-ethoxy]"
piperidine
1330 4.4-(1\2'-cyclohexylendioxy)-2,2,6,6-tetramethyl-1-[r'-(4'-oxiranylmeth^^^^
ethoxy]-piperidine
134.) 77,9.9-Tetramethyl-8-[1-(4-oxiranylmethoxy--phenyl)-ethoxy]-1,4-dioxa-8-a2a-
spiro[4.5]decane-2,3-dicarboxyiic acid dimethyl ester
135.) 8,8.10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-a2a-
spiro[5.5]undecane
136.) 3,3,8.81,0,10-Hexamethyl'9-[1-(4-oxiranylmethoxy-phenyI)-ethoxy]-1.5-dioxa'9--a2a-
spiro[5.5]undecane
137.) 3-Ethyl-3,8,8.10.10-pentamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-'
a2a-spiro[5.5]undecane 138.)3,3-Diethyl-8,8,10,10-etramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-
a2a-spiro[5.5]undecane
139.) 3,8.8,10,10-Pentamethyl-9-[1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-3-propyl-1,5-dioxa-9-
a2a-spiro[5.5]undecane
140.) 3-Butyl-3-ethyl-8,8,10,104etramethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,5-
dioxa-9-a2a-spiro[5.5]undecane
141.) 2,2,4,4"Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,16-dioxa-3-aza-
dispiro[5.2.5.2]hexadec-11-ene
142.) {3,8,8,10,10-Pentamethyl-9-I1 -(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dJoxa-9-aza-
spiro[5.5]undec-3-yl}-methanol
143.){3-Ethyl-8,8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9^
aza-spiro[5.5]undec-3-yl}-methanol
144.) 3-Methoxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-
1,5-dioxa-9-a2a-spiro[5.5]undecane
145.)3-Cyclohexyloxymethyl-3,8,8,10,10-p6ntamethyl-9-[1-(4-oxiranylmethoxy-phenyl)^
ethoxy]-1,5"dioxa-9-a2a-spiro[5.5]undecene

146.)3-Benzyloxymethyl-3,8,8,10,10-pentamethyl-9-[1-(4-oxiranylmethoxy"phenyl)^^^
1.5-dioxa-9-aza-spiro[5.5]undecane
147.) Acetic acid 3.8,8,10.10-pentamethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,5-
dioxa-9-aza-spiro[5.5]undec-3-ylmethyl ester
148.) Octanedioic acid bis-{3,8,8,10,10-pentamethy!-9-[1-(4-oxiranylmethoxy"phenyl)-
ethoxy]-1.5-dioxa-9-aza-spiro[5.5]undec-3-ylmethyl} ester
149.) 1\6'-Bis-{8.8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-9-
aza-spiro[5.5]undec-3-ylmethyl}-oxyhexane
150.) 3,8,8,10,10-Pentamethyi-9-[1 -(4-oxiranylmethoxy-phenyi)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane-3-carboxylic acid methyl ester
151.) 8,8,10,10-Tetramethyl-9-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,5--dioxa-9-aza-
spiro[5.5]undecane-3,3-dicarboxylic acid diethyl ester
1520 3,3-Bis-{8.8,10,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-
aza}-spiro[5.5]undecane
153.) 2,2,4,4-Tetramethyl-3-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-7,12-dioxa-3-aza-
spiro[5.6]d odec-9-ene
7. A compound according to claim 6 of formula la, lla or Ilia which is
4,4-Dibutoxy-2,6-diethyl-2,3,6-trimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]"piperidine;
7,9-Diethyi-67,9-trimethyl-8-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,4-dioxa-8-aza-spiro-
[4.5]decane; 8,10-Diethyl-3,3,7,8,10-pentamethyi-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-
aza-spiro[5.5]undecane; {8,10-Diethyl-3,7,8,10-tetramethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undec-3-yl}-methanol; {3,8,10-Triethyl-7,8,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1.5-dioxa-9-aza--
spiro[5.5]undec-3-yl}-methanol; 4.4-Dibutoxy"2,2-diethyl-6,6-dimethyl-1-[1-(4-oxiranylmethoxy-phenyl)-ethoxy>piperidine;
7,7-Diethyl-9,9-dimethyl-8-[1-(4-oxiranylmethoxy"phenyl)-ethoxy]-1,4-dioxa-8-aza-
spiro[4.5]decane; 8,8-Diethyl-3,3,10,10-tetramethyl-9-I1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane; {8.8-Diethyl"3,10,10-trimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undec-3-yl}-methanol;

{3,8,8-Triethyl-10,10-dimethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-di
spiro[5.5]undec-3-yl}-methanol;
4,4-Dibutoxy-2,2,6,6-tetramethyl-141-(4-oxiranylmethoxy-phenyl)-ethoxy]-piperidin
7,7,9,9-Tetramethyl-8-[1-(4-oxiranyImethoxy-phenyl)-ethoxy]-1,4-dioxa-8-a2a"
spiro[4.5]decane;
3,3,8,8,10,10"Hexamethyl-9-[1-(4-oxiranylmethoxy-phenyl)-ethoxy]-1,5-dioxa-9-aza-
spiro[5.5]undecane.

Y and Y* together form one of the bivalent groups -C(R1)(R2)-CH(R3)-, CH(R1)-CH2-C(R2)(R3)". -CH(R2)-CH2-C(Ri)(R3)-. -CH2-C{R1)(R2)-CH(R3)-, o-phenylene, 1,2-cyclohexyliden,

9. A polymerizable composition according to claim 8, wherein the ethylenically unsaturated monomers or oligomers are selected from the group consisting of styrene, substituted

styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.
10. A polymerizable composition according to claim 9, wherein the ethylenically unsaturated
monomers are styrene. a-methyl styrene, p-methyl styrene, butadiene, methylacrylate,
ethylacrylate, propylacrylate, n-butyl acrylate. tert.-butyl acrylate and acrylnitrii.
11. A polymerizable composition according to claim 8. wherein the compound of formula la,
Jia or Ilia is present in an amount of from 0.01 mol-% to 20 mol-% based on the monomer.

15. Use of a compound of formula la, lla or Ilia according to claim 1 for polymerizing
ethylenically unsaturated monomers.
16. Use of a compound of formula la, lla or Ilia according to claim 1 for terminating the
anionic polymerization of a diene or vinyl monomer.

18. A polymerizable composition substantially as herein described with reference to the
accompanying drawings.
19. A process for preparing an oligomer substantially as herein described with reference to the
accompanying drawings.

Documents:

1061-chenp-2003-abstract.pdf

1061-chenp-2003-claims filed.pdf

1061-chenp-2003-claims granted.pdf

1061-chenp-2003-correspondnece-others.pdf

1061-chenp-2003-correspondnece-po.pdf

1061-chenp-2003-description(complete)filed.pdf

1061-chenp-2003-description(complete)granted.pdf

1061-chenp-2003-form 1.pdf

1061-chenp-2003-form 26.pdf

1061-chenp-2003-form 3.pdf

1061-chenp-2003-form 5.pdf

1061-chenp-2003-other documents.pdf

1061-chenp-2003-pct.pdf

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Patent Number

212202

Indian Patent Application Number

1061/CHENP/2003

PG Journal Number

02/2008

Publication Date

11-Jan-2008

Grant Date

26-Nov-2007

Date of Filing

10-Jul-2003

Name of Patentee

M/S. CIBA SPECIALTY CHEMICALS HOLDING INC

Applicant Address

Klybeckstrasse 141 CH-4057 Basel

Inventors:

#	Inventor's Name	Inventor's Address
1	FUSO, Francesco	Bienenweg 8 CH-4106 Therwil

PCT International Classification Number

C07D 211/94

PCT International Application Number

PCT/EP2001/013071

PCT International Filing date

2001-11-12

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	00811191.6	2000-12-14	EUROPEAN UNION