MXPA99006330A - Method of controlling polymer molecular weight and structure - Google Patents

Abstract

This invention concerns the preparation of polymers of low polydispersity and/or controlled molecular weight and architecture employing living free radical polymerization initiated by an alkoxyamine initiator or nitroxide plus, optionally, a free radical initiator;the polymer produced thereby;selected nitroxide and alkoxyamine initiators;and a process for making the initiators;the polymeric products being useful in protective coatings.

Description

METHOD FOR CONTINUING THE MOLECULAR WEIGHT AND THE STRUCTURE OF A POLYMER BACKGROUND OF THE INVENTION This invention relates to the preparation of polymers with low polydispersity and / or molecular weight and controlled architecture by the use of polymerization with latent free radicals, initiated by an appropriate alkoxyamine or nitroxide-initiator combination. It also refers to new compounds useful in these polymerizations and methods for their preparation. Latent radical polymerization based on the use of alkoxyamine initiators was invented by Rizzardo et al and is described in U.S. Patent No. 4,581,429. Recent publications by Georges et al (Trends Poly Sci., 1994, 2, 66-72), Hawker (J. Am. Chem. Soc., 1994, 116, 11185-11186) and others have described the application of the methodology to the synthesis of polystyrenes with a narrow polydispersity. The nitroxide component in these latter studies is most frequently 2, 2, 6, 6-tetramethylpiperidine-l-oxyl (TEMPO) or one of its derivatives. Now they have Ref .: 30674 discovered the advantages of polymerizations with free radicals, latent, mediated by nitroxide using imidazoline nitroxides (1) as defined below in addition: Formula 1) The characteristics of a latent polymerization are discussed by Quirk and Lee (Polymer International 27, 359 (1992)) who give the following experimentally observable criteria: 1. The polymerization proceeds until all the monomer is consumed. The additional addition of monomer results in continuous polymerization. 2. The number average molecular weight (or the average degree in polymerization number) is a linear function of the conversion. 3. The number of polymer molecules (and active centers) is a constant that is substantially independent of the conversion. 4. The molecular weight can be controlled by the stoichiometry of the reaction. 5. Polymers with a narrow molecular weight distribution are produced. 6. Block copolymers can be prepared by the sequential addition of the monomer. 7. Polymers with chain end functional groups can be prepared in quantitative yield.

BRIEF DESCRIPTION OF THE INVENTION This invention provides a polymer of formula (2) below: wherein R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, aryl substituted from 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; groups R that are in a cis position with respect to each other can jointly form a ring of 4-8 members; X is selected from the group consisting of hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; M is one or more monomer units selected from the group consisting of styrene, substituted styrene, alkyl acrylate, alkyl methacrylate, substituted alkyl acrylate, substituted alkyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamide , N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylamide, isoprene and butadiene; m is an integer greater than 1; Y is a residue derived from a species that initiates the polymerization of free radicals or is selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, substituted alkoxy of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms; substituted aryl of 6 to 18 carbon atoms, aroyloxy of 6 to 18 carbon atoms, aroyloxy substituted of 6 to 18 carbon atoms, (C? ~ C? 8 alkoxy) carbonyloxy, (C6-C? 8 aryloxy) carbonyloxy, and anions of sulfate radicals; and All substituents are independently selected from the group consisting of epoxy, hydroxy, alkoxy of 1 to 18 carbon atoms, acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, cyano, silyl, halo, and dialkylamino of 1 to 18 carbon atoms . The polymers of this invention have low polydispersity which provides improved flow properties in the function or solution. In addition, the presence of the nitroxyl terminal group allows the formation of cloque copolymers by heating the preformed polymer with a different monomer. Alternatively, the terminal nitroxyl group can be reduced or chemically modified to give a polymer for a more desirable terminal group. The term "polymer (s)" as used herein includes graft block copolymers and other complex architectures. The specific monomers or co-monomers from which M is derivable include the following: methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-acrylate, -ethylhexyl, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, functional methacrylates, styrene acrylates selected from glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, triethylene glycol methacrylate ol, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), N, N-dimethylaminoethyl acrylate, N, N-acrylate diethylaminoethyl, triethylene glycol acrylate, methacrylamide, N-ethylacrylamide, N, -dimethylacrylamide, N-tert-butyl methacrylamide, NN-butyl methacrylamide, N-methylolmethacrylamide, NN-ethylolmethacrylamide, N-tert-butyl-acrylamide, NN-butylacrylamide, N-methylolacrylamide , N-ethylolacrylamide, vinylbenzoic acid (all isomers), diethylaminostyrene (all isomers), alpha-methylvinyl-benzoic acid (all isomers), diethylamino-alpha-methylstyrene (all isomers), p-vinylbenzensulfonic acid, sodium salt of p-vinylbenzenesulfonic acid, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethyl-silipropyl methacrylate, methacrylate of dibutoximetilsilipropilo methacrylate diisoproproximetilsililpropilo methacrylate, dimethoxysilylpropyl methacrylate dietoxisilipropilo methacrylate dibutoxisilipropilo methacrylate, diisopropoxysilylpropyl acrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxisililpropilo acrylate dimetoximetilsililpropilo acrylate dietroximetilsilipropilo acrylate dibutoximetilsililpropilo acrylate, diisopropoxymethylsilylpropyl, dimethoxysilylpropyl acrylate, dietoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, butadiene, isoprene, chloroprene. This invention provides a process for preparing the polymers of Formula (2), which comprises contacting reagent (i) with one or both of reagents (ii) and (iii) wherein: (i) is at least one M monomer; (ii) is at least one imidazoline nitroxide of the formula (I) and a source of free radicals Y »; and (iii) at least one alkoxyamine selected from the formula wherein: R, R1, R2, R3, X, M and Y are as defined above; Z is a group having at least one carbon atom such as Z-carbon-centered radical. It is capable of initiating the free-radical polymerization of the monomer (M), Y and the reaction conditions are selected so that the Y-portion (M) n-0 in the compounds of the formula (2) formed from the reactants (i) and (ii) undergo easy homolysis; and the reaction conditions are selected such that the Z-O portion and the Z (M) n-0 portion formed by reacting (i) with (iii) undergoes easy homolysis; n is an integer of 1 or greater; and Y * can be produced thermally from the monomer (when one of the monomers is styrene or a styrene derivative) or from a free radical initiator or combination of initiators. The use of the nitroxides of the formula 1 (or the "corresponding alkoxyamines") offers significant advantages over the nitroxides previously used in the nitroxide-mediated polymerization: homopolymers, statistical copolymers and block copolymers having a controlled molecular weight, a narrow weight distribution and a defined terminal group functionality can be synthesized.The method can also be adapted to the preparation of multiblock and graft polymers and others of more complex architecture.With an appropriate selection of substituents R, R1, R2, R3 , and X, (defined later in the present), the use of nitroxides (1) offers lower polydispersities and greater latent character than, for example, TEMPO and derivatives.

Additional advantages are that (a) the nitroxides (1) and the derivatized alkoxyamines are synthesized from easily available precursors by a simple experimental route; (b) undergo minor side reactions (eg, disproportion of radical propagation with nitroxide or chain transfer to nitroxide); and (c) non-volatile. This provides an advantage over many of the more commonly used nitroxides such as TEMPO and many of its derivatives, and di-t-butyl-nitroxide, which are odorous. The process can be run continuously or in batches and can be carried out as a solution, emulsion, suspension, or bulk polymerization using procedures well known in the art. If Z is a polymer chain (e.g., Y (M) n-) then the product can be a block copolymer. Block copolymers can also be prepared by the sequential addition of different monomers or monomer combinations. Graft copolymers and polymers of more complex architecture can be prepared from appropriately designed precursors containing multiple nitroxide moieties.

The reaction conditions of the polymerization include temperatures in the range from about 20 ° C to 300 ° C, preferably from 40 ° C to 250 ° C, and most preferably from 50 ° C to 150 ° C, ambient pressures up to 100 atmospheres and optional solvent (s) compatible with the monomer / polymer system. The polymers made by the process of this invention are also characterized by having terminal functional groups - which are derived from the Y and / or Z portions and the nitroxide fragment (1). This functionality will include hydroxy; carboxylic acid (-COOH) and its esters; cyano; isocyanate; epoxy; halo, amino; and similar. This invention relates to particular nitroxides of the formula (1) useful in the polymerization process wherein: R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; groups R that are in a cis position with respect to each other can jointly form a ring of 4-8 members; X is selected from the group consisting of, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; with the condition that R, R1, R2, R3 and X are not all methyl. The preferred nitroxides selected from the above group are the following: wherein X is selected from the group consisting of alkyl, optionally substituted alkyl, benzyl; Y wherein X is alkyl of 1 to 18 carbon atoms - This invention also relates to novel alkoxy acids of the formula (3) wherein: R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; and R groups that are in a cis position with respect to each other can jointly form a 4-8 membered ring; X is selected from the group consisting of, hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; and Z is a group having at least one carbon atom and the carbon radical Z 'is capable of initiating the free radical polymerization of the monomer (M). Suitable groups Z are -C (Me) 2Ph, -C (e) 2CN, -C (Me) (CN) CH 2 CH (Me) 2, -C (Me) (CN) (substituted alkyl), -C (Me) ) 2C02alkyl, -C (Me) 2C02H, -C (Me) 2CH2C (Me) 3, -C (Me) 3, -C (Me) HPh and Y (M) "-. This invention also includes a process for making the nitroxides of the formula (1). The process comprises reacting an amino nitrile and a ketone to form a cyanoimine, and reacting the imine with hydrogen sulfide to produce linear thioamide, and cyclizing the linear thioamide to form a 2, 2, 5, 5-tetrasubstituted-imidazolidin- 4-thione, and convert the cyclic thioamide to the corresponding cyclic amide and then convert the final imidazoline-4 -one to the nitroxide. In particular, the process for making nitroxides of the formula (1) comprises: a (i) preparing a colorless solution of ammonium sulfide, aqueous containing sodium thiocyanate to the titrant an aqueous solution of ammonium sulfide containing ammonium polysulfide with Sodium cyanide under nitrogen; (ii) sequentially adding an aminonitrile and a ketone to the aqueous solution of ammonium sulfide 'under nitrogen; (iii) add the base and then neutralize; and (iv) oxidizing the reaction product of step (iii) to form the nitroxide. Alternatively, in step (ii) of the process, the aminonitrile can be replaced by a mixture of ketone, ammonium chloride, and sodium or potassium cyanide. In another embodiment of this process, the process is stopped before the addition of sodium tungstenate and the corresponding cyclic amine / amide is isolated. Step (ii) of the process can be carried out at a temperature between 20 ° and 80 ° C, preferably between 30 ° and 60 ° C, and more preferably at 54 ° C. The base is preferably sodium carbonate or sodium hydroxide, more preferably sodium hydroxide. Any suitable acid can be used for neutralization, the preferred acid is sulfuric acid. In this process, the concentration of hydrogen peroxide is preferably 20 to 50%, more preferably 30%. Preferred oxidants for the conversion of amine to nitroxide are H202 / tungstenate, dimethyldioxirane, H202 / acetic acid. DETAILS OF THE INVENTION The nitroxides most commonly used in free radical, latent, nitroxide-mediated polymerizations have been 2,2,6,6-tetfamethylpiperidin-N-oxyl (TEMPO) and derivatives of this compound and di-t-butyl-nitroxide ( diBuNO).

TEMPO di? UNO these and other nitroxides / alkoxyamines which are conventionally used in free radical, latent, nitroxide-mediated polymerizations are inherently high cost. Substantial improvements in the cost for the entire process can therefore be achieved by the use of nitroxide (1), a material obtainable from a cheap precursor by the simple experimental route. It has been found that, in various polymerizations, the use of certain 2, 2, 5, 5, 5-tetraalkylimidazolin-4-one-l-oxyl derivatives in the nitroxide-mediated polymerization offers lower polydispersities for polymers that are obtained with other used nitroxides for this purpose (for example, TEMPO and derivatives or diBuNO). In the context of the present invention, low polydispersity polymers are those with polydispersities that are significantly lower than those produced by conventional free radical polymerization. In conventional free radical polymerization, polydispersities (polydispersity is defined as the ratio of number-average and weight-average molecular weights - Mw / M n) of the polymers formed are typically in the range of 1.6-2.0 for minors conversions (< 10%) and may be substantially greater than this for higher conversions. The polydispersities obtained with the present invention are usually less than 1.5, often less than 1.3, with the appropriate choice of nitroxides (1) / alkoxyamines and the reaction conditions, may be less than 1.1. Low polydispersity can be maintained at high conversions. The polydispersities in the nitroxide-mediated polymerization are believed to depend on a number of factors. These include (i) the rate of exchange between the active and non-active species that are greatly determined by the rate of binding homology between N-0 and the adjacent portion-for the alkoxyamines comprised either as starter species or formed during the polymerization (for a discussion of this topic see Moad and Rizzardo, Macromolecules 1995, 28, 8722-8); and (ii) the importance of the various side reactions For the polymerizations comprising nitroxide (1) the rate of binding homology between N-0 and the adjacent portion and the polydispersities obtained depend on the particular nitroxide or alkoxyamine used and in particular of the substituents, R, R1, R2, R3, and X. A preferred group of nitroxides in this context are the compounds of N-alkyl-2,2,5,5-tetraalkylimidazolin-4-one-l-oxyl (s) say, (1) X = alkyl, for example, 2,5-bis (spirocyclohexyl) -3-methylimidazolidin-4-one-1-oxyl (N0-88-Me)) which is seen to offer the smaller polydispersities is polymerizations of styrene or copolymerizations thereof Also preferred within each class (X = alkyl and X = Y) are those (1) with the most bulky RRs The following are structures of nitroxides described herein: It is believed that an important side reaction in the nitroxide-mediated polymerization is the disproportion between nitroxide and the propagating species. It has been found that in the polymerization with methyl methacrylate (MMA), the use of 2, 2, 5, 5-tetraalkylimidazolin-4-one-1-oxyl derivatives offers low polydispersities and good latent character for polymerizations. While not wishing to be bound by a particular mechanism, these advantages are believed to be in part a consequence of the imidazoline nitroxides of 5-membered rings that provide a higher combination ratio: disproportion to the reaction with propagation radicals than 6-membered (i.e. TEMPO) or open-chain (i.e. diBuNO) ring nitroxides. These routes are illustrated in scheme 1 for polymerization with MMA. It is noted that the products of the disproportionation reaction, the vinyl terminated macromolar and the hydroxylamine (H-Q) can also further react under polymerization reaction conditions that lead to further complications. Clearly, the minimization of this lateral reaction is important to obtain the polymerization with latent characteristics.

Scheme 1 disproportion í < combination? ¡Q.

In scheme 1, Q is a nitroxide. Similar side reactions have also been shown to occur during the polymerization of styrene mediated by nitroxide. In the polymerization of nitroxide at 90 ° C, the rate constants for the transfer of hydrogen from the propagation species to NO-67 and TEMPO in relation to the propagation velocity constant have been measured as 0.18 and 0.43, respectively. In the synthesis of nitroxides of the formula (1), the product nitroxide can be isolated by conventional means, preferably from the reaction mixture by filtration or by extrusion with an organic solvent that is substantially insoluble in water. It has been found that the ammonium polysulfide reacts with either aminonitrile or cyanide ion, thereby reducing the amount of cyanide below the stoichiometric ratios, thereby decreasing the total yield. This can be prevented by the previous addition of cyanide ion to the polysulphide decolorization point and innocuous thiocyanate formation. The process described herein for the synthesis of nitroxides (1, X = H) is as follows: (1) The alkoxyamines of this invention are made from the compounds of the formula (1) when combined with Z ", for example, by the procedure of example 43 and by that described in Macromolecules, 1997, 30, 6445-6450. The alkoxyamines of this invention can be made by a variety of methods such as the alkylation of the hydroxyamines derived from nitroxides of the formula (1); and the alkoxylation of the compound of the formula (6) as will be obvious to one skilled in the art.

EXAMPLES General Experimental Conditions The monomers were purified (to remove inhibitors) and distilled instantaneously immediately before use. Degassing was achieved by repeated cycles of freezing-evacuation-thawing. Once the degassing was completed, the ampoules were sealed to the flame under vacuum and completely immersed in an oil bath at the specified temperature for the specified times. The conversion percentages were calculated gravimetrically.

The structures of the polymers and the block copolymers have been verified by the application of appropriate chromatographic and spectroscopic methods. Gel permeation chromatography (GPC) has been used to establish the molecular weight and molecular weight distribution (polydispersity) of the polymers. Liquid chromatography from Waters Associates equipped with differential refractometer and ultraestiragel columns of 106, 105, 104, 103, 500 and 100 A was used. Tetrahydrofuran was used as eluent (flow rate 1.0 ml / min). Molecular weights are provided as polystyrene equivalents. The terms Mn, Mw and M w / M n are used to indicate the average molecular weights in number and weight and polydispersity, respectively. NMR spectroscopy was used to clarify the structures of the polymers and provide evidence for the terminal groups of the polymers. The NMR spectra were obtained on a Bruker spectrometer (200 MHz) and CDCI3 was used as solvent.

EXAMPLES 1-5 Polymerization of Styrene These examples show that the narrow polydispersity polystyrene can be prepared with NO-88. Polydispersity is initially 1.3 and is reduced to 1.2 during the course of the experiment.

Procedure A concentrated solution was prepared which contained styrene (9.10 g, 87.5 mmol), benzoyl peroxide (70.7 mg, 0.29 mmol). Separately, NO-88 (29.1 mg, 0.12 mmol) was added to each of the 5 vials. Then an aliquot (2 ml) of the concentrated solution was added to each vial, and the contents of the ampoules were degassed by 3 cycles of freezing, evacuation, thawing, sealing and heating at 130 ° C during the designated times. The results are shown in Table 1.

Table 1 Polymerization of bulk styrene in the presence of NO-88 and benzoyl peroxide at 130 ° C.

Example Time / h M n M "/ M n n (calc) to% of Convb 1 2 508 1.31 235 1.5 2 4 1626 1.27 784 5.0 3 8 4911 1.26 5334 34.0 4 23 7061 1.21 10559 67.3 72 12291 1.20 14136 90.1 a M n (cale) = [converted monomer] / ([BPO] 2) b% conversion evaluated from the NMR spectra LH EXAMPLES 6-11 MMA Polymerizations The following section reports results of polymerizations of methyl methacrylate in the presence of the azo-initiator, 2, 2'-Azobis (2,4-dimethylvaleronitrile) (VazoR-52) and different nitroxides. The results for NO-67 (Example 6-9) and NO-88 (Examples 10-12) are shown in Tables 2 and 3, respectively. The effectiveness of these nitroxides is compared with other nitroxides in Table 4. Additional sampling after 1 hour of the reaction time shows little or no increase in molecular weight or conversion. The 5-membered ring nitroxides (NO-67 and NO-88) give the most favorable results (narrow polydispersity). In all cases, the product is believed to be a MMA macromonomer formed by loss of a hydrogen atom from the nitroxide spreading species (ie, reaction by disproportion instead of combination).

Procedure A concentrated solution containing MMA was prepared (10 ml, 9.36 g) VazoR-52 (13.43 mg, 0.054 mmol), and NO-67 (14.2 mg, 0.077 mmol). 3 ml of the concentrated solution was transferred to each of the three ampoules which were then degassed through 3 freeze-thaw cycles, sealed, and heated to 90 ° for the indicated times.

Table 2: Polymerization of bulk MMA with VazoR-52 and NO-67, 90 ° C.

Example Time / h \ 'M n M w / M n of Conva Cale M n 6 0.5 31737 1.68 24.9 30305 7 1 .38021 1.47 251.3 30730 8 6 35709 1.57 38.2 46411 at% conversion evaluated from the mass of the polymer obtained.

Procedure A concentrated solution was prepared containing MMA (9 ml, 8.42 g) VazoR-52 (12.08 mg, 0.049 mmol), and NO-88 (17.16 mg, 0.069 mmol). 3 ml of the concentrated solution was transferred to each of the three ampoules which were then degassed through 3 freeze-thaw cycles, sealed, and heated to 90 ° for the indicated times.

Table 3 Polymerization of bulk MMA with VazoR-52 and NO-88, 90 ° C.

Example Time / h n M w / M n% of Conva Cale Mn 9 0.5 308 1.03 0.7 866 1 6472 1.44 6.4 7822 11 6 7890 1.44 5.4 6590 at% conversion evaluated from the mass of the polymer obtained.

TABLE 4 Table 4 Polymerizations of MMA after 1 hour at 90 ° C with VazoR-52 and Nitroxide1 1 reaction conditions similar to those used for experiments described in Tables 2 and 3.

Vazo is a registered trademark of E.l. di Pont de Neumours and Company. The particular VAZ0R compositions referred to herein comprise the following compounds: VAZ0R 2,2'-azobis (2,4-dimethylvaleronitrile), VAZ0R 2, 2'-azobisisobutyronitrile, VAZOR 2, 2'-azobis (2-methylbutyronitrile), and VAZOR 1, 1 '-azobis (cyanocyclohexane).

Examples 12 to 27 Polymerization of Styrene A series of styrene polymerizations was carried out in the presence of N0-67, "NO-88, and the N-substituted imidazoline nitroxides, NO-67-Me, NO-88-Me, NO-67-Bn and NO-67-nBu) and the benzoyl peroxide initiator The polymerization was carried out at 130 ° C for a period of time indicated in Table 5 below.The results are summarized in Table 5.

Procedure The following six solutions were prepared (i) Styrene (5 ml), NO-88 (72.75 mg) benzoyl peroxide (35.35 mg). (ii) Styrene (10 ml), NO-88-Me (154 mg) benzoyl peroxide (70.70 mg). (iii) Styrene (5 ml), NO-67 (56.75 mg) benzoyl peroxide (35.35 mg). (iv) Styrene (10 ml), NO-67-Me (122.00 mg) benzoyl peroxide (70.70 mg). (v) Styrene (5 mi), NO-67-Bn (84.32 mg) benzoyl peroxide (35.35 mg). (vi) Styrene (5 ml), NO-67-nBu (73.88 mg) benzoyl peroxide (35.35 mg). Aliquots (2 ml) of these solutions were transferred into ampoules and the contents were degassed by three freeze-thaw cycles. The ampules were then sealed and "heated at 130 ° C for the times indicated in Table 5. The ampules were cooled, opened and the reaction mixture reduced in vacuo to a residue that was dried to constant weight and analyzed. by GPC.

Table 5 Molecular weight data per GPC of polystyrene prepared via polymerizations of styrene with nitroxide and benzoyl peroxide at 130 ° C Example Nitroxides Time h M, MJK i Cspv. 12 NO-88 23 16047 1.23 99.0 13 NO-88-Me 2 780 1.18 5.9 14 NO-88-Me 4 3115 1.13 20.9 15 NO-88 «Me 8 8765 1.09 56.0 16 NO-88-Me 18 16271 1.09 96.0 17 NO-88- e 23 16300 1.09 99.0 18 O-67 23 16043 1.49 99.0 19 NO-67-Me 2 502 1.36 5.0 20 NO-67-Me 4 1380 1.29 9.9 21 NO-67-Mt 8 2499 1.34 22.4 22 NO-67-Me 18 4693 1.29 49.4 23 NO-67-Me 23 8075 1.24 60.0 24 NO-67-Bn 4 1402 1.23 9.1 25 NO-67-Bn 18 5102 1.28 47.4 26 NO-67-pBu 4 1430 1.22 8.8 27 NO-67-nBu 18 60'3 1.25 53.0 The proton-NMR spectrum of a polystyrene sample (M n 3115) of example 14 has the signal ad 2.90 ppm clearly indicating the presence of N-methyl from the terminal group 2,5-bis (spirocyclohexyl) -3-methylimidazolidin -4 -one-1-oxyl (NO-88Me).

Examples 28-31 Acrylate Polymerization The polymerization of tert-butyl acrylate in tubes sealed at 120 ° C was carried out using the alkoxyamine, 1- (2-tert-butyl-butoxy-1-phenylethoxy) -2,5-bis (spirocyclohexyl) -3- methylimidazolin-4-one as an initiator-ternate. This example demonstrates how acrylate polymers with low polydispersity can be obtained (1.3-1.4). Two groups of experiments were carried out: (i) A concentrated solution of alkoxyamine (71.3 mg), tert-butyl acrylate (1.0 ml) in benzene (4.0 ml) was prepared. Aliquots (2.0 ml) were transferred in ampoules (x2) and the contents were degassed by three freeze-thaw cycles. The ampules were then sealed and heated at 120 ° C for 24 hours and 49 hours, respectively. The results are shown in Table 6 below.

Table 6 Polymerizations of tert-butyl acrylate in the presence of alkoxyamine in benzene at 120 ° C Example Time / h Mn M "/ Mn% Conv 28 24 1525 1.39 28.0 29 49 1830 1.32 34.4 The proton-NMR spectrum of a sample of poly (tert-butyl acrylate) from example 28 (M n 1525) had ad 7.10 ppm signals indicating the presence of the phenyl group (compare d 7.30 ppm of the original alkoxyamine used) and d 2.90 ppm indicating the presence of the N-methyl group of NO-88-Me. (ii) A concentrated solution of alkoxyamine (71.3 mg), tert-butyl acrylate (5.0 ml) was prepared. Aliquots (2.0 ml) were transferred in ampoules (x2) and the contents were degassed by three freeze-thaw cycles. The ampules were then sealed and heated at 120 ° C for 24 hours and 49 hours, respectively.

The results are shown in Table 7 below.

Table 7 Polymerizations of bulk tert-butyl acrylate in the presence of alkoxyamine at 120 ° C Example Time / h Mn Mw / Mn% Conv 24 8272 1.51 28.6 31 49 9005 1.41 39.8 Examples 32-33 Synthesis of Block Copolymers The following two examples [polystyrene-block-poly (4-methylstyrene) and polystyrene-block-poly (n-butyl acrylate)] demonstrate the synthesis of block copolymers. The samples were prepared by heating a polystyrene of narrow polydispersity (derived from NO-88-Me) Mn 8765, M w / M n 1.09; see Table 5, example 15) with 4-methylstyrene and n-butyl acrylate, respectively. The results are excellent in both cases and give low polydispersity block copolymers.

Example 32 Polystyrene-block-poly (4-methylstyrene) To a vial, a sample of polystyrene (250 mg) (Mn8765, M w / Mn 1.09, Example 15) was dissolved in 1 ml of 4-methylstyrene (freshly distilled) The contents of the vial were degassed and sealed under vacuum Subsequently, the mixture was polymerized at 130 ° C for 18 hours and gave a polystyrene-block-poly (4-methylstyrene) of narrow polydispersity (0.85 g, 95% conversion Mn36872, M w / M n 1.14.

Example 33 Polystyrene-block-poly (n-butyl acrylate) To a vial, a sample of polystyrene (250 mg) (Mn8765, M u / M n 1.09, Example 15) was dissolved in 1 ml of n-butyl acrylate (freshly distilled). The contents of the ampule were degassed and sealed under vacuum. Subsequently, the mixture was polymerized at 130 ° C for 18 hours and gave a polystyrene-block-poly (n-butyl acrylate) of narrow polydispersity (0.608 g, 68% conversion Mn21526, M w / M n 1.29.

Example 34-36 Synthesis of Statistical Copolymers A series of styrene / acrylonitrile copolymerizations (molar ratio 62:38, the azeotropic composition) in the presence of N-substituted imidazolidinone nitroxides NO-88-Me, NO-67-Me and NO-67-Bn. The experiments were carried out thermally by doing at 130 ° C for 18 hours. The results are summarized in Table 8.

Procedure A freshly distilled styrene (I) concentrated solution (7.27 g) of acrylonitrile (2.27 g) was prepared. Each vial contains concentrated solution (2 g) and nitroxide (1.23 x 10-4 mol). The contents were degassed, sealed and heated at 130 ° C for 18 hours.

Table 8: GPC data of styrene / acrylonitrile copolymers prepared thermally at 130 ° C with different nitroxides.

Examples 37-42 Synthesis of Nitroxides of the Formula (1) The following examples 37-38 illustrate the new process for the synthesis of nitroxides (1, where X = H).

Example 37 Preparation of 2,5-diethyl-2,5-dimethylimidazolidin-4-one-1-oxyl (NO-67) Preparation of 2,5-diethyl-2, 5-dimethylimidazolidin-4-thione A 1-liter, four-necked round bottom flask equipped with a mechanical stirrer, thermocouple thermometer, nitrogen sparger, rinse scrubber with bleach, and condensers reflux was charged with 17.4 g of ammonium chloride (0.32 mol), 35.9 g of AN-67 (0.3 mol, 87% of 2-amino-2-methylpropionitrile in water, XH NMR (ppm) of freshly distilled AN-67 in D20: 1.03 (t, 3H), 2.45 (s, 3H), 1.75 (q, 2H), 23.1 g of 2-butanone (0.32 mol), and 132.9 g of 20% solution of ammonium sulfide (0.39 mol) As the solution was heated to 50 ° C, a slight exotherm occurred which increased the temperature to 65 ° C and some of the ammonium hydrosulphide was sublimed into the condenser.After 20 minutes, the temperature declined to 55 ° C and remained stable. So for 18 hours, an oily liquid layer formed on top of the aqueous solution for the first 5 minutes. lfuro was ruled out in the first minute; this was caused by the reaction of cyanide ion with sulfur to give colorless thiocyanate ion and a decrease in production. The next day, the solution was cooled to -15 ° C, 25 g of NaCl were added to salify the thione, filtered cold to give 39 g of the product. The mother liquor was treated with 10 g of K2C03 to precipitate an additional 5 g of the product. K2C03 is more effective in the salification of thiones, amides, and nitroxides than NaCl. The solids were combined to give 4 4 g (80% yield) of thione after 2 days of air drying, m.p. 58-64 ° C. IR (nujol) 1540 cm-1; NMR 1H ppm (D20) 0.96 (overlap t, 12H, CH3 in 4), 1.39, 1.40, 1.42, 1.43 (4 singles, total of 12H, CH3 for four isomers, ie, 2 pairs of cis-trans), 1.75 (m, 8H, 4 CH2 groups).

Calculated Analysis for Combustion Observations: C9H? 8N2S • 0.1 (H20) C 57.46 57.90 • H 9.75 9.24 N 14.89 14.94 S 17.05 16.68 The thione can be purified by column chromatography on silica gel using hexane to dilute a fragrant fraction before the thione. The effect of temperature variation and concentration of reactants on the production and reaction rate was examined in a sealed NMR tube using D20 as a solvent and sodium tosylate as an internal standard. What was observed was a slight decrease in the concentration of the starting materials and a slight increase in the concentration of the product. The reaction time can be reduced from 16 hours at 50 ° C to 6 hours at 80 ° C. The compound, 2-methyl-2-aminobutyrothioamide, was not observed indicating that this alicyclic intermediate reacts with MEK in a rapid step to produce the cyclic product.

Preparation of 2, 5-diethyl-2, 5-dimethylimidazolidin-4-one "A 5-liter four-necked round bottom flask equipped with a mechanical stirrer, thermocouple thermometer, was charged with 250 ml of water and 43.3 g ( 0.232 mol) of 2, 5-diethyl-2, 5-dimethylimidazolidin-4-thione. In order to dissolve the thione, 1.8 g of NaOH was added. The solution was cooled to 0-2 ° C with a dry ice-acetone bath. The flask is equipped with 2 additional funnels. Simultaneously, a solution of 16.7 g of NaOH in 100 ml of water (total of 18.5 g or 0.464 mol of used NaOH) was added through one of the funnels and 105 ml (0.928 mol) of 30% H202 were added. through the other funnel. The reaction mixture was stirred rapidly and extensive cooling was required during the addition. The 5 liter flask was used to provide a large surface area for efficient cooling of the exothermic reaction. The heat of the reaction was 296.2 Kcal / mol; 124. The addition was completed in 2 hours; the mixture was stirred for an additional half hour. At the end of this time, the TLC indicated that Tiona did not remain. Then, 27.9 g of NaHS03 (0.172 mol) were added to rapidly quench the excess peroxide; this reaction is also somewhat exothermic (increase in temperature from 26 to 43 ° C). The reaction mixture was transferred to a 2 liter round bottom flask and the solvent was removed with a rotary evaporator (vacuum pressure) to give a white residue. The residue was extracted with 850 ml of boiling ethanol. Then, 50 ml of toluene were added to the solution and 130 ml of the water azeotrope / ethanol / toluene were distilled to remove any remaining water. The solution was cooled and filtered to remove a small amount (about 1 g) of Na 2 SO and then the ethanol was removed on the rotary evaporator to give a syrup which crystallized on cooling to room temperature. The yield was 37.5 g (95%) m.p. 58-64 ° C. IR (Nuj ol) 1705, 1659 eral-. XH NMR (CDC13 + D20) ppm (combination of equal amounts of 2 groups of cis-trans pairs) 0.95-0.98 (m, 12H, CH3 in 4 ethyl), 1.27, 1. 31, 1.34, 1.38 (4 s, total 12H, 4 CH3), 1.50-1.70 (m, 8H, CH2 in 4 ethyl). The singles at 1.34 and 1. 38 collapses to a singlet in D20, but now they enter 6H.

Annals of Ca lculation for Combustion Observations: C9H? 8N20) C 63. 4 9 63.07 H 10. 66 10.01 N 16. 45 16.23 0 9. 4 0 9.49 Preparation of 2, 5-diethyl-2, 5-domethylimidazolidin-4-one-1-oxyl A one liter polymer jar equipped with a mechanical stirrer, odor trap filled with bleach, heating blanket, reflux condenser and thermometer of charge thermocouple with 153.3 g (0.45 mol) of 20% ammonium sulfide solution. To this solution was added 1.47 g (0.03 mol) of NACN to react with the ammonium polysulfide impurity in the ammonium sulphide solution. Then, 35.9 g of AN-67 (0.3 mol) and 21.7 g of 2-butanone (0.3 mol) were added. The solution was stirred and heated under nitrogen at 55 ° C for 18 hours; some ammonia evaporated. Two liquid layers are formed; the lower layer is thioamide. The volume of the reaction mixture is now 200 ml. The mixture was cooled to room temperature and a solution of 36 g of NaOH (0.9 mol) in 100 ml of Water was added. The solution was cooled to 0 ° C and 306 g (2.7 mol) of 30% H202 were added dropwise with stirring and cooling to 4-10 ° C. The addition took 65 minutes. After stirring for 1 hour, the solution was brought to pH = 7 by the addition of a solution of 58 g of concentrated H2SO4 and 56 g of water at 13 ° C. Then, 68 g (0.6 mol) of H20 at 30% were added. No exotherm was noted at this time. To this, 5.0 g of Na2 0 .H20 were added. The total reaction volume is 763 mi. An initial greenish-yellow color (pertungstate ion) is replaced by a deep yellow color (nitroxides). The temperature of the mixture rose from 13 to 31% centigrade for 3-1 / 2 hours. The next day, the solution was filtered to give 27.5 g (40% yield) of nitroxide, M.F. 117-122 ° C. It was subsequently found that 1-3 of AN-67 is destroyed by hydrolysis and irreversible reaction with sulfur to form thiocyanate ion. If this is taken into account, the production is 82%; Each step is approximately 93%. The solubility in NMP is at least 1: 1. IR (nujol) 1720, 1675 cm-1; (toluene solution) 1713.3 cm-1. Nitroxide exhibits a triplet in the ESR. Aliquots of the reaction mixture were removed at selected times and diluted with a known amount of xylene. The int rred intensity of the ESR triplet was plotted as a function of time when the peroxide concentration doubled or the tungstate ion concentration was increased to 3. The data are fitted to parabolas. The initial slopes of the lines are obtained by differentiating the empirically adjusted curves to determine the slope of the line and solving the equation obtained in x =; the speed law at 24 ° C was found to be k = k [H202] ° -5 + -1 [04"] 1 - 0+ - 1 Calculated Analysis for Combustion Observation: CgHis zS'O.KH; > 0) C 57.75 57.71 H 9.16 8.82 N 14.92 15.21 0 17.04 17.28 Example 38 Preparation of 2,5-bis (spirocyclohexyl) imidazolidin-4-one-l-oxyl (N0-88) Preparation of 2,5-bis (spirocyclohexyl) imidazolidin-4-thione. A 2-liter, 4-necked, round bottom flask equipped with a mechanical stirrer, heating blanket, reflux condenser, thermocouple thermometer, nitrogen sparger and outlet tube connected to an odor trap filled with bleach was charged with 132.9 g (0.39 mol) of 20% ammonium sulfide solution followed by 0.5 g of NaCN to decolorize the polysulfide impurity in the ammonium sulfide solution. Under a positive nitrogen flow, 16.1 g (0.3 mol) of ammonium chloride and 14.7 g (0.3 mol) of NaCN were added. The temperature of the solution dropped to 8 ° C. Then, 58.9 g (0.6 mol) of cyclohexanone which has been previously deoxygenated by bubbling nitrogen through it for 10 minutes were added dropwise with stirring for 5 minutes. The temperature increased to 30 ° C. The temperature of the solution was lowered to 47 ° C, at which point the external heating was stopped, and the reaction spontaneously allowed to exotherm at 63 ° C. The temperature was then maintained at 55 ° C. After 1 hour, 1.0 g of NacN and a mild exotherm at 63 ° C followed by a return at 55 ° C were noted. An additional 1.0 g of NaCN was added 30 minutes later; this caused only a mild exotherm at 58 ° C. The temperature was maintained at 55 ° C overnight. A sample of the resulting thick suspension was then removed and divided into two parts. A part was dissolved in acetone, and checked by TLC (CH2C12: acetone 9: 1); two species were present. The other part was filtered to give white crystals, m.p. 225-230 ° C. The precipitate was filtered in place with a filter stick to avoid handling the odorous mixture. The insoluble precipitate of thione; the other impurity was cyclohexanone, which remained in the filtrate. The tiona was washed by adding 300 ml of water to the flask, stirring, and then stirring the water through the filter stick. IR (nujol) 1520 cm-1.

Preparation of 2,5-bis (spirocyclohexyl) imidazolin-4-one To the wet crystalline residue obtained above 24 g (0.6 mol) of NaOH dissolved in 300 ml of water were added in the same flask. The crystals failed to dissolve; the crystals were finally dissolved by the addition of 485 ml of methanol. The solution did not show the characteristic exotherm in the addition of 30% hydrogen peroxide at 0-5 ° C. The temperature of the solution was increased 40 ° C; the addition of peroxide is exothermic at this temperature. After adding 147 g (4 x 0.32 mol) of 30% peroxide, the solution temperature was maintained at 55 ° C for 30 minutes and then it was stirred at room temperature overnight; by TLC, the mixture consisted of amide and thione. The mixture was filtered and the precipitate was washed with 3 x 100 ml of water. To the filtrate were added 57 g of peroxide [total used peroxide = 204 g (1.8 mol)] and the solution was concentrated at 40 ° C. A slight exotherm occurred at 46 ° C. To help oxidation, 1 g of Na2W04.H20 was added. After 15 minutes, a white precipitate began to deposit. The mixture was allowed to stir at room temperature for 18 hours and then filtered. By IR, both precipitates were identical and combined and dried with air, m.p. 216-220 ° C, 58.5 g (88% yield based on cyclohexanone). IR (nujol) 1690 cm-1.

Preparation of 2,5-bis (spirocyclohexyl) imidazolidin-4-one-l-oxyl A solution of acetone of 260 ml of dimethyl. 0.08 M dioxide (0.0208 mol), prepared as above, was treated with 2.3 g of 2,5-bis (spirocyclohexyl) imidazolidin-4-one dissolved in 75 ml of chloroform (previously free of ethanol preservatives when washing with 2 x 20 of water and dried over magnesium sulfate) and allowed to react at room temperature overnight. The preparation was repeated using 1.7 g of amide and 270 ml of 0.0721 M dimethyldioxirane solution. Removal of the ethanol preservative is necessary to prevent the ethanol from oxidizing to acetaldehyde by the dimethyldioxirane-nitroxide system. • The solvent was stirred in the rotary evaporator, the residue (4.2 g) was dissolved in 400 ml of hot benzene, filtered to remove a trace of insoluble material, the filtrate was reduced to 100 ml, reheated to put all the crystals in solution, and left to crystallize overnight at room temperature. The yellow crystals were collected by filtration and dried in an oven at 75 ° C for 10 hours to give 2.4 g of nitroxide, m.p. 178-183 ° C. IR (nujol) 1707 cm-1.

Calculated Analysis for Combustion Observations: C9H? 8N2S • 0.1 (H20) C 65.79 65.67 H 8.92 8.84 N 11.80 11.71 OR 13.487 13.31 Examples 39-42 Synthesis of N-substituted imidazolidinone nitroxides The following examples 39-42 are illustrated in the process for the synthesis of new nitroxides (1, X = alkyl). The new N-substituted imidazolidinone nitroxides were prepared according to the following general procedure. A suspension of imidazolinone nitroxide (5.5 mole NO-67 or 1.6 mole of NO-88) and sodium hydride (1.33 molar equivalent, 80% dispersion in oil) was allowed to stir under a nitrogen atmosphere in acetonitrile solvent ( 20 ml for NO-67 or 10 ml for NO-88) at room temperature for 15 minutes, and then the required amount of alkyl halide was added. (1:20 molar equivalents). After evaporation and purification by column chromatography, the corresponding new N-substituted imidazolinone nitroxide was generally obtained in good yield (45-93%).

Example 39 Preparation of 2,5-bis (spirocyclohexyl) -3-methylimidazolidin-4-one-l-oxyl (NO-88-Me) The title compound, NO-88-Me isolated me as a yellow solid after column chromatography (Kieselgel-60, 70-230 mesh, ethyl acetate / n-hexane 1: 4 as eluent) (89.7% yield) ). Melting point, 103-105 ° C.

MS (CI): 252 (M + 1, 100%), 251 (M +, 30.7), 237 (87.6), 236 (12.3), 235 (29.3), 222 (24.5), 221 (40.6), 196 (18.7), 193 (10.5), 142 (24.7), 140 (53.9), 112 (16.0) and 99 (23.5).

Example 40 Preparation of 2,5-diethyl-2,3,5-trimethylimidazolidin-4-one-l-oxyl (NO-67-Me) The title compound, NO-67-Me (45.6% yield) after column chromatography (Kieselgel-60, 70-230 mesh, etiXo acetate / n-hexane 1: 3 as eluent) as a yellow liquid. MS (Cl): 200 (M + 1.43.0%), 199 (M +, 16.0), 186 (23.5), 185 (40.0), 171 (58.0), 170 (34.0), 155 (23.0), 149 (20.2) ), 141 (11.6), 140 (15.6), 128 (10.0), 126 (16.1), 116 (13.7), 112 (14.4), 111 (12.7), 100 (12.2), 73 (52.0).

Example 41 Preparation of 2,5-Diethyl-2, 5-dimethyl-3-benzylimidazolidin-4-one-l-oxyl (NO-67-Bn) The title compound, NO-67-Bn was isolated (93.0% yield) after column chromatography (Kieselgel-60, 70-230 mesh, ethyl acetate / n-hexane 1: 5 as eluent) as a yellow solid. Melting point, 64-65 ° C. MS (Cl): 276 (M + 1, 56.7%), 275 (M, 22.0), 262 (22.0), 261 (100.0), 247 (62.6), 245 (M-NO, 26.0), 231 (86.0) , 218 (5.3), 190 (12.3), 170 (15.0), 162 (24.6), 126 (20.1), 102 (4.0), 91 (21.5) and 72 (4.0).

Example 42 Preparation of 2,5-Diethyl-2, 5-dimethyl-3-n-butylimidazolidin-4-one-l-oxyl (NO-67-nBu) The title compound, NO-67-nBu was isolated (87.0% yield) after column chromatography (Kieselgel-60, 70-230 mesh, ethyl acetate / n-hexane 1: 9 as eluent) as a liquid yellow. MS (Cl): 242 (M + l, 74.0%), 241 (M +, 38.3), 227 (100.0), 213 (86.7), 211 (45.0), 198 (12.0), 197 (88.0), 184 (M -nBu, 7.6), 170 (27.0), 156 (16.3), 128 (27.0), 126 (30.0), 116 (4.3), 98 (8.0) and (7.6).

Example 43 Synthesis of Alkoxyamine of the Formula (3) Preparation of 1- (2-tert-butoxy-l-phenylethoxy) -2,5-bis (spirocyclohexyl) -3-methylimidazolin-4 -one The alkoxyamine of the title, 1- (2-tert-butoxy-1-phenylethoxy) -2, 5-bis (spirocyclohexyl) -3-methylimidazolin-4-one was prepared by treating l- (2-tert-butoxy-1-phenylethoxy) -2,5-bis (spirocyclohexyl) -4-methylimidazolin-4- ona, alkoxyamine (mp 244-247 ° C, obtained from the reaction of di-tert-butyl peroxyoxolate, styrene and nitroxide NO-88) with excess methyl iodide in the presence of sodium nitride in dimethyl sulfoxide solvent ( Scheme 3). The product was isolated as a white solid at 93% yield, m.p. 129-131 ° C (aqueous MeOH). The alkoxyamine product has improved solubility against its unmethylated alkoxyamine and is readily soluble in common organic solvents such as ethyl acetate, chloroform, acetone, hot methanol. 1R NMR (CDC13) d (ppm) 0.40-2.60 (m, 20H, cyclohexyl-CH2), 1.10 (s, 9H, tert-butyl-CH3), 2.90 (s, 3H, N-CH3), 3.30 (dd, 1H, (CH3) 3COCH), 3.66 (dd, 1H, (CH3) 3COCH), 4.69 (dd, 1H, CH (Ph) ON) and 7.25 (br s, 5H, phenyl-H).

Scheme 3 a) NaH / DMSO, excess methyl iodide, at room temperature.

It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property:

Claims (12)

1. A polymer of the formula: characterized in that: R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; groups R that are in a cis position with respect to each other can jointly form a ring of 4-8 members; X is selected from the group consisting of hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; M is one or more units of monomers selected from the group consisting of styrene, substituted styrene, alkyl acrylate, alkyl methacrylate, substituted alkyl acrylate, "substituted alkyl, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methacrylate" alkylacrylamide, N-alkylmethacrylamide, N, N-dia1kylacrylamide, N, N-dialkylmethacrylamide, isoprene and butadiene; m is an integer greater than 1; Y is a residue derived from a species that initiates free radical polymerization or selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, substituted alkoxy of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms, aroyloxy of 6 to 18 carbon atoms, substituted aroyloxy of 6 to 18 carbon atoms, and all substituents are independently selected from starting from the group consisting of epoxy, hydroxy, alkoxy of 1 to 18 carbon atoms, acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, cyano, silyl, halo, and dialkylamino of 1 to 18 carbon atoms.

2. A process for preparing the polymers of claim 1, characterized in that it comprises contacting the reagent (i) with one or more of the reactants (ii) and (iii) wherein: (i) is at least one monomer M; (ii) is at least one nitroxide of the formula (1) (1) and a source of free radicals Y »; and (iii) at least one alkoxyamine selected from the formula wherein R, R1, R2, R3 are each independently selected from the group consisting of "alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms, the R groups which are in a germinal position with respect to each other can jointly form a ring of 4-8 members, the R groups which are in a cis position with respect to each other can jointly forming a 4-8 membered ring: X is selected from the group consisting of hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms, acyl, X and R can form a 5-8 membered ring, X and R3 can form a 5-8 membered ring; M is one or more monomer units selected from the group consisting of styrene, substituted styrene, alkyl acrylate, alkyl methacrylate, substituted alkyl acrylate, substituted alkyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamide , N-alkylmethacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, isoprene and butadiene; m is an integer greater than 1; Y is a residue derived from a species that initiates the polymerization of free radicals or is selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, substituted alkoxy of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms; substituted aryl of 6 to 18 carbon atoms, aroyloxy of 6 to 18 carbon atoms, aroyloxy substituted of 6 to 18 carbon atoms, (C? ~ Cie alkoxy) carbonyloxy, (C6-C? aryloxy) carbonyloxy, and anions of sulfate radicals; and all substituents are independently selected from the group consisting of epoxy, hydroxy, alkoxy of 1 to 18 carbon atoms, acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, cyano, silyl, halo, and dialkylamino of 1 to 18 carbon atoms . Z is a group having at least one carbon atom and is such that the carbon radical Z # is capable of initiating the free radical polymerization of the monomer (M); and Y and the reaction conditions are selected so that the Y (M) n-0 portion in the compounds of the formula (2) formed of the reactants (i) and (ii) undergoes easy homolysis; Z and the reaction conditions are selected so that the Z-O portion and the portion Z (M) n-0 formed by reacting (i) and (ii) undergoes easy homolysis; and n is an integer of 1 or greater

3. Nitroxides of the formula characterized in that R, R, R, R are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, aryl substituted from 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; groups R that are in a cis position with respect to each other can jointly form a ring of 4-8 members; X is selected from the group consisting of, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; with the proviso that R, R1, R2, R3 and X are not all methyl.

. A nitroxide according to claim 3, characterized in that it is selected from the group (4) wherein X is selected from the group consisting of alkyl, optionally substituted alkyl, benzyl,; Y wherein X is alkyl of 1 to 18 carbon atoms,

An alkoxyamine of the formula characterized in that R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, aryl substituted from 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; and "R groups that are in a cis position with respect to each other can jointly form a 4-8 membered ring, X is selected from the group consisting of, hydrogen, alkyl of 1 to 18 carbon atoms, alkyl substituted from 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms, acyl, X and R can form a ring of 5-8 members, X and R3 can form a ring of 5-8 members, and Z is a group having at least one carbon atom and the carbon radical Z 'is capable of initiating the free radical polymerization of the monomer (M).

6. An alkoxyamine according to claim 5, characterized in that Z is selected from the group consisting essentially of -C (Me) 2Ph, -C (Me) 2CN, C (Me) (CN) CH 2 CH (Me) 2, - C (Me) (CN) (substituted alkyl), -C (Me) 2CO2alkyl, -C (Me) 2CO 2 H, -C (Me) 2CH 2 C (Me) 3, C (Me) 3, -C (Me) HPh and Y (M) n-; wherein Y is a residue derived from a species that initiates free radical polymerization or is selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, alkoxy of 1 to 18 carbon atoms, substituted alkoxy of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms; substituted aryl of 6 to 18 carbon atoms, aroyloxy of 6 to 18 carbon atoms, substituted aroyloxy of 6 to 18 carbon atoms, (Ci-Ciß alkoxy) carbonyloxy, (C6-Ci8 aryloxy) carbonyloxy, and radical anions of sulfate; and all substituents are independently selected from the group consisting of epoxy, hydroxy, alkoxy of 1 to 18 carbon atoms, acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, cyano, silyl, halo, and dialkylamino of 1 to 18 carbon atoms .

7. A method for the nitroxide of the formula (1): wherein: R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; R groups that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; and R groups that are in a cis position with respect to each other can jointly form a 4-8 membered ring; X is selected from the group consisting of, hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; characterized in that it comprises the steps of preparing a colorless aqueous ammonium sulfide solution containing sodium thiocyanate to the titrant an aqueous solution of ammonium sulfide containing ammonium polysulfide with sodium cyanide under nitrogen; (ii) sequentially adding an aminonitrile and a ketone to the aqueous solution of ammonium sulfide under nitrogen; (iii) add the base and then neutralize; and (iv) oxidizing the reaction product of step (iii) to form the nitroxide.

8. The method according to claim 7, characterized in that: R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; and R groups that are in a cis position with respect to each other can jointly form a 4-8 membered ring; X is selected from the group consisting of, hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; with the proviso that R, R1, R2, R3 and X are not all methyl.

9. The method according to claim 7, characterized in that it comprises stopping the process before step (iv) and isolating the reaction product from step (iii), and then practicing step (iv).

10. The method according to claim 7, characterized in that the intermediate isolation of the reaction product of step (iii) before the reaction in step (iv).

11. An aqueous, colorless solution of ammonium sulfide, characterized in that it contains sodium thiocyanate and substantially no ammonium polysulfide.

12. A method for making an alkoxyamine according to claim 5, characterized in that it comprises one of steps (i) to (iii): (i) adding Z »to the nitroxide (ii) adding Z-O to the amine (iii) alkylating the hydroxylamine derived from a nitroxide of the formula (1); wherein: R, R1, R2, R3 are each independently selected from the group consisting of alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; groups R that are in a germinal position with respect to each other can jointly form a ring of 4-8 members; and R groups that are in a cis position with respect to each other can jointly form a 4-8 membered ring; X is selected from the group consisting of, hydrogen, alkyl of 1 to 18 carbon atoms, substituted alkyl of 1 to 18 carbon atoms, aryl of 6 to 18 carbon atoms, substituted aryl of 6 to 18 carbon atoms; acyl; X and R can form a ring of 5-8 members; X and R3 can form a ring of 5-8 members; and Z is a group having at least one carbon atom and the carbon radical Z 'is capable of initiating the free radical polymerization of the monomer (M).