MXPA98007601A - Start of polymer chain by free radicals, with non-reactient insaturations - Google Patents

Abstract

This invention relates to a method by which olefinically unsaturated molecules, which are otherwise not polymerizable, can be homopolymerized or copolymerized with conventional monomers through the use of chain transfer cobalt catalysts. The resulting macromonomers contain a terminal functional group and a terminal double bond at the other end of the chain.

Description

START OF POLYMER CHAIN BY RADICAT.?! < - T.TO ^ Eg, _ON NON-REACTIVE INSATURATIONS FIELD OF THE INVENTION This invention relates to a method by which olefinically unsaturated organic molecules, which are otherwise non-reactive and nonpolymerizable, can be used to initiate polymer chains from free radical monomers by the use of cobalt catalyst. chain transfer, and the products of that method.

A i '-_ I r_ii) ENTES DE LA TÉCNICA It is well known that there are many olefinically unsaturated organic compounds which are essentially inert to a free radical polymerization process, either to form homopolymers or to form copolymers with conventional monomers such as methacrylates, acrylates, styrene and the like. The expression "are essentially inert" is considered to mean in the present that these olefinically unsaturated molecules are not homopolymerized and that they copolymerize with conventional monomers at levels less than 10 mole percent, REF. 28193 even when they are present in an excess of ten times relative to conventional monomers. U.S. Patent No. 5,587,431 describes a method for preparing unsaturated polymer compositions in the terminal part by restarting the termini of an unsaturated oligomer in the terminal part with an additional chain transfer catalyst.

(CTC) for additional oligomerization. Several publications have discussed the copolymerization of methacrylic dimers, but no mention is made of the "reboot" of the dimers involved.

See D, M. Haddleton, et al., Macromolecules 29 (1996), p. 481ff; T. P. Davis, et al., Macromol. Theory Simul. 4 (1995), p. 195ff; T. P. Davis, et al., J. Macromolecular Science - Rev. Macromol. Chem. Phys., C34 (2) (1994), p. 243ff. US-A-3 281 497 discloses a process for preparing cobalt complexes of carboxylic acids using peroxides. In the present application, AZO initiators are requested. O-A-8 703 605 discloses polymers and copolymers of certain conventional monomers. The invention described herein demonstrates the copolymerization of otherwise non-polymerizable organic molecules (hereinafter referred to as "UO"), instead of oligomers or macromonomers, and the production of functionalized monomers and macromonomers (with functional groups) from you are UO BRIEF DESCRIPTION OF THE INVENTION This invention relates to an improvement in a process for the free-radical polymerization of one or more monomers, hereinafter referred to as "conventional monomers" (CM). The polymers formed have end groups terminated in vinyl. The polymerization is initiated by a functional group derived from an olefinically unsaturated organic molecule. The CM useful in the process have the formula CH2 = CXY wherein X is selected from the group consisting of CH3 and CH2OH; And it is selected from the group consisting of OR, 02CR, halogen, C02H, COR, C02R, CN, CONH2, CONHR, CONR2 and R "; R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted aryl, unsubstituted and substituted heteroaryl, substituted aralkyl and unsubstituted, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino , isocyanate, sulfonic acid and halogen, and the carbon number in the alkyl groups is from 1 to 12, and R 'is selected from the aromatic group consisting of unsubstituted and substituted aryl, unsubstituted and substituted heteroaryl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanate, acid sulphonic, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin, and halogen; by contacting the CMs with a chain transfer agent containing cobalt and a free radical initiator at a temperature from about 25 ° C to 240 ° C; the improvement, which includes adding an olefinically unsaturated organic molecule, UO, to the structure wherein R1 and R3 are each independently selected from the group (I) consisting of -CH (O), -CN and halogen, and of group (II) consisting of -C (0) OR5, -C (0) NRsR7, -CR8 (O), -C (0) OC (0) R9, -CiONR ^ COR11, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R1 or R3 are selected from group II, R1 and R3 can optionally form a cyclic structure; and R2 and R4 can each be independently selected from the group (III) consisting of H, -CH (O), -CN and halogen, and of group (IV) consisting of -C (0) 0R5, -C ( 0) NR6R7, -CR8 (0), -C (O) OC (O) R9, -C (O) NR ^ COR11, -0C (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R2 or R4 are selected from group IV, R2 and R4 can optionally form a cyclic structure; R5, R6, R7, R8, R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are CLC, and the substituents on the alkyl or substituted aryl do not contain functionality which can substantially interfere with free radical polymerization (e.g., groups that are known to be free radical chain terminators) such as thiols or nitroxides). In another embodiment, at least one of R1 and R2 are hydrogen, and R3 and R4 each independently are selected from the group (I) consisting of -CH (O), -CN and halogen, and of group (II) which consists of -C (0) OR5, -C (0) NR6R7, -CR8 (0), -C (0) OC (0) R9, -C (O) NR ^ COR11, -OC (0) R12, - OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R3 or R4 are selected from group II, R3 and R4 optionally can form a cyclic structure; or a mode wherein: R3 and R4 can each be selected independently of the group (III) consisting of H, -CH (O), -CN and halogen, and of group (IV) consisting of -C (0) OR 5, -C (0) NR 6 R 7, -CR 8 (0), -C (O) OC (O) R 9, -C (O) NR 10 COR 1: L, -OC (0) R 12, -OR 13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R3 or R4 are selected from group IV, R1 and R2 may optionally form a cyclic structure; R5, Rs, R7, R \ R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are C? -C_2 / Y and substituents on the alkyl or substituted aryl do not contain functionality which can substantially interfere with the free radical polymerization (for example, groups known to be terminators). chain by free radicals such as thiols or nitroxides). This invention is further related to the products manufactured by the above process. This invention also relates to a macromonomer consisting of an olefinically unsaturated organic molecule and at least one conventional monomer, the macromonomer is represented by wherein m ranges from 1 to 100, preferably 2 to 20, and more preferably 2 to 10, and wherein the initial olefinically unsaturated organic substance can be represented by the formula (A) R ^ C CR 3JRr > _ (A) wherein R1, R2, R3 and R4 can each be independently selected from the group consisting of H, -CH (O), -CN, halogen, -C (0) OR5, -C (0) NR6R7 , -CR8 (O), -C (O) OC (0) R9, -CO R ^ COR11, -0C (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; R1 and R3 or R2 or R4 can be combined in a cyclic structure when R1, R2, R3 or R4 are -C (0) 0R5, -C (0) NR6R7, -CR8 (0), -C (0) OC ( O) R9, -C (O) NR10COR1: L, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl or substituted aryl; and with the additional proviso that at most two of R1, R2, R3 and R4 can be H; Rs, R6, R7, R8, R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are c_ "ci2 < - And the substituents on the alkyl or substituted aryl do not contain functionality which may substantially interfere with the free radical polymerization (for example, groups known to be chain terminators by free radicals such as thiols or nitroxides); And it is selected from the group consisting of OR, 02CR, halogen, C02H, COR, C02R, CN, C0NH2, CONHR, CONR2 and R1; R is selected from the group consisting of unsubstituted and substituted alkyl, substituted and unsubstituted aryl, unsubstituted and substituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, substituents being the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanate, sulfonic acid and halogen; and the number of carbons in the alkyl groups is from 1 to 12; and R 'is selected from the aromatic group consisting of unsubstituted and substituted aryl, unsubstituted and substituted heteroaryl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, amino primary, secondary amino, tertiary amino, isocyanate, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin, and halogen; the conventional monomer (CM) is selected from the group consisting of styrenes, acrylates, vinylpyridines, methacrylates, α-methylstyrenes, vinylpyrrolidones, chloroprene and other monomers known to undergo catalytic chain transfer in the presence of cobalt catalysts. This invention also relates to macromonomers as described above with the proviso that both R1 and R2 can not be H at the same time.

DESCRIPTION T-TI AT.T ._. T-A. OF THE INVENTION The macromonomers of this invention are formed by the polymerization of non-reactive, olefinically unsaturated organic molecules (UO), with other conventional monomers (in the present CM) in the presence of cobalt complexes capable of carrying out chain transfer catalyst (CTC) ). By "UO" is meant generally an internal olefinic monomer or other unsaturated monomeric species which does not homopolymerize or copolymerize appreciably with conventional monomers (CM) which are known to be CTC-for example, methacrylates, methacrylonitrile, α-methylstyrene and similar, as well as their fluorinated analogues. By "does not copolymerize to an appreciable degree" is meant that these olefinically unsaturated organic molecules copolymerize with conventional monomers at levels less than ten mole percent relative to the conventional monomer even when present in a tenfold excess relative to the monomers conventional Often these molecules will inhibit copolymerizations.

Preferred metal chain transfer catalysts for use in the preparation of the present materials are cobalt (II) and (III) chelates. Examples of such cobalt compounds are described in U.S. Patent No. 4,680,352, U.S. Patent No. 4,694,054, U.S. Patent No. 5,324,879, and WO 87/03605, published June 18, 1987, U.S. Patent No. 5,362,826, and U.S. Patent No. 5,264,530. Other useful cobalt compounds (porphyrin cobalt complexes, phthalocyanines, tetraazoporphyrins and cobaloximes) are respectively described in Enikolopov, N.S. , et al. , patent of USSR 664,434 (1978); Golikov, I., et al. , USSR patent 856, 096 (1979); Belgovskii, I. M., USSR patent 871,378 (1979); and Belgovskii, I.M., USSR patent 1,306,085 (1986). These catalysts operate at contracted diffusion speeds and are effective at part-per-million concentrations. Examples of these cobalt (II) and cobalt (III) chain transfer catalysts include, but are not limited to, those represented by the following structures: Co (II) (DPG-BF2) 2 J = K = Ph, L = ligand Co (II) (DMG-BF2) 2 J = K = Me, L = ligand C? (II) (EMG-BF2) 2 J = Me, K = Et, L = ligand Co (II) (DEG-BF2) 2 J = K = Et, L = ligand Co (II) (CHG-BF2) 2 J = K = - (CH2) 4-, L = ligand QCo (III) (DPG-BF2) 2 J = K = Ph, R = alkyl L = ligand QCo (III) (DMG-BF2) 2 J = K = Me, R = alkyl L = ligand QC? (III) ( EMG-BF2) 2 J = Me, K = Et, R = Alkyl L = ligand QCo (III) (DEG-BF2) 2 J = K = Et, R = Alkyl L = ligand QCo (III) (CHG-BF2) 2 J = K = - (CH2) 4- R = Alkyl L = ligand QCo (III) (DMG-BF2) 2 J = K = Me, R = halogen, L = ligand L may be a variety of neutral ligands commonly known in coordination chemistry. Examples include water, amines, ammonia and phosphines. The catalysts also include cobalt complexes of a variety of porphyrin molecules such as tetraphenylporphyrin, tetraanisylporphyrin, tetramesityl-porphyrin and other substituted species. Q is an organic radical (for example alkyl or substituted alkyl); Preferred Q groups are isopropyl, 1-cyanoethyl and 1-carbomethoxyethyl. When Co CTC catalysts are present, the chains are initiated with a single UO followed by polymerization of the conventional monomers until CTC takes place. When the CTC occurs, the polymer chain ends' by loss of a hydrogen atom, producing a terminally unsaturated monomer, - the hydrogen atom is transferred by the CO catalyst to a new UO, so a new chain is started of polymer. Therefore, macromonomers contain a functional group derived from the UO and a terminal double bond at one end (vinylidene unsaturation). By vinylidene unsaturation derived from subtraction of hydrogen atom from CM is meant the group YPC = CH2 wherein Y is selected from the group consisting of OR, 02CR, halogen, C02H, COR, C02R, CN, C0NH2, CONHR, CONR2 and R '; R is selected from the group consisting of unsubstituted and substituted alkyl, substituted and unsubstituted aryl, unsubstituted and substituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, substituents being the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanate, sulfonic acid and halogen; and the number of carbons in the alkyl groups is from 1 to 12; and R 'is selected from the aromatic group consisting of unsubstituted and substituted aryl, unsubstituted and substituted heteroaryl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, amino primary, secondary amino, tertiary amino, isocyanate, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin, and halogen; and P is a polymeric or oligomeric group resulting from the addition of a conventional monomer to polymeric or oligomeric radicals. The general reaction scheme can be summarized as equation 1: UO + CM + Co CTC - UOx (CM) ra + (CM) p (1) The designated coproduct (CM) p is unavoidable, but its presence can be minimized by reaction conditions where the reagent is deleted. The polymerization degrees (m) and (p) are controlled by the level of added CTC of Co, but m ranges from 1 to 100, preferably from 2 to 20, and more preferably from 2 to 10, while p varies from 2. to 100, and is generally similar to m. In cases where a certain minimum level of copolymerization occurs, the general reaction scheme can be described by equation 2: UO + CM + Co CTC - UO ^ CM) ™ + (UO) n (CM) m + (CM) p (2) The degree of polymerization (n) is controlled by the reactivity ratio of UO and CM, but n is generally 2 and is rarely greater than. For the most useful products, the resulting macromonomers will contain one UO and two to 20 CM; therefore, the molar ratio of UO: CM will vary between about 1: 2 to about 1:20. The control experiments described within the examples demonstrate this. The general formula for the UO is: wherein R1 and R3 are each independently selected from the group (I) consisting of -CH (O), -CN and halogen, and of group (II) consisting of -C (0) OR5, -C (0) NR6R7, -CR8 (O), -C (0) OC (0) R9, '-C (O) NR10COR1: L, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R1 or R3 are selected from group II, R1 and R3 can optionally form a cyclic structure; and R2 and R4 can each be independently selected from the group (III) consisting of H, -CH (O), -CN and halogen, and of group (IV) consisting of -C (0) OR5, -C ( 0) NR6R7, -CR8 (0), -C (O) OC (O) R9, -C (O) NR ^ COR11, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R2 or R4 are selected from group IV, R2 and R4 can optionally form a cyclic structure; Rs, R6, R7, R8, R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are C? -Ci2 / and the substituents on the alkyl or substituted aryl do not contain functionality which may substantially interfere with the free radical polymerization (for example, groups known to be chain terminators) by free radicals such as thiols or nitroxides). such a conventional monomer (CM) is one or more monomers that are selected from the group consisting of methacrylates, methacrylonitrile, ..-methylstyrene, vinylpyrrolidone, chloroprene and other monomers known to undergo catalytic chain transfer in the presence of cobalt transfer catalysts. chain; the chain transfer cobalt catalysts are selected from the group consisting of cobalt (II) or (III) chelates, cobalt porphyrins, cobalt phthalocyanines, cobalt tetraazoporphyrins, cobalt glyoximes, cobalt cobaloximes and other cobalt chelates (II) and cobalt (III) suitable. By the phrase "can form a cyclic structure" is meant that the groups R (ie, R1, R2, R3, R4) which are attached to the same C of the group C = C, are "cis" in relation to " = "and may be linked to form a cyclic structure. This can be illustrated in the following structures: It is recognized by those familiar with the art that these structures are representative and that there is no reason, for example, that the foregoing of R2 and R4, or Rx and R2 does not represent the cyclic portion in the structures. Example 7 later illustrates this. Preferred conventional monomers (CM) are: acrylonitrile, methacrylonitrile, vinyl methyl ketone, 4-chlorostyrene, 4-chloromethylstyrene, 2,3-dimethylstyrene, 3-dichlorostyrene, 4-bromostyrene, 4-hydroxystyrene, 4-methoxystyrene, 4-oxymethylstyrene, 4-bromomethylstyrene, 4-styrenesulfoinic acid, sodium salt of 4-styrenesulfoinic acid, 4-styrenesulfoinyl chloride, methyl acrylate, ethyl acrylate, propyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, dodecyl acrylate, glycidyl acrylate, acrylamide, N, N'-dimethylacrylamide, bisacrylamide, 2-acrylamido- 2-methyl-l-propanesulfonic acid, acrylic acid, sodium salt of acrylic acid, zinc salt of acrylic acid, acryloyl chloride, [2- (acryloyloxy) ethyl] -trimethylammonium chloride, 2-ethyloxyethyl acrylate, acrylate 2- (N, N '- dimethylamino) ethyl, methacryloyl chloride, methacrylic anhydride, acrylic anhydride, [2- (methacryloyloxy) ethyl] trimethylammonium chloride, 2- (methacryloyloxy) ethyl methacrylate, 2- (methacryloyloxy) ethylacetoacetate, [2- (methacryloyloxy) chloride] propyl] trimethylammonium, vinyl chloride, 4-vinylbenzoic acid, vinyl acrylate, vinyl methacrylate, vinyl chloroformate, vinylpyridine, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alphamethylstyrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilyl-propyl methacrylate, methacrylate dibutoxymethylsilylpropyl, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, isopropenyl butyrate, isopropenyl acetate, isopropenyl benzoate, isopropenyl chloride, isopropenyl fluoride, isopropenyl bromide, itaconic acid, anhydride itaconic, dimethyl itaconate, methyl itaconate, N-tert-butylmethylacrylamide, N, n-butylmethylacrylamide, N-methyl-olmethylacrylamide, N-ethyl-ol-methylacrylamide, isopropenylbenzoic acid (all isomers), d imethylaminoalphamethylstyrene (all isomers), paramethylamphemethylstyrene (all isomers), diisopropenylbenzene (all isomers), isopropenylbenzenesulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, ethyl 2-hydroxymethylmethacrylate, propyl 2-hydroxymethylacrylate (all isomers) ), Butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate, isobornyl 2-hydroxymethylacrylate, methyl 2-chloromethylacrylate, ethyl 2-chloromethylacrylate, propyl 2-chloromethylacrylate (all isomers), 2-butyl chloromethylacrylate (all isomers), 2-ethylhexyl 2-chloromethylacrylate, isobornyl 2-chloromethyl acrylate, chloropropene and vinylpyrrolidone. The olefinically unsaturated organic molecules (UO) preferred are: butenonitrile (all isomers), pentenonitrile (all isomers), methyl butenecarboxylate (all isomers), ethyl butenecarboxylate (all isomers), propyl butenecarboxylate (all isomers), butyl butenecarboxylate (all isomers), 2-ethylhexyl butenecarboxylate (all isomers), methyl pentenecarboxylate (all isomers), ethyl pentenecarboxylate (all isomers), perfluoro (propylvinyl) ether, methyl cinnamate, ethyl cinnamate, propyl cinnamate (all isomers), cinnamonitrile, methylmaleic anhydride, cyclopenten-1-one, cyclohexen-1-one, cyclohepten-1-one, maleate dimethyl, dimethyl fumarate, diethyl maleate, methyl crotonate, ethyl crotonate, crotonaldehyde, crotononitrile, methyl fumaronitrile, diphenylethylene (all isomers), triphenylethylene, methyl octadencen-2-oate, octadecen-2-oatoxyethyl, Methyl hexadecene-2-oleate, ethyl hexadecene-2-olea, coumarin, coumarin-3-methyl carboxylate and methylitaconic anhydride. The UO can be used as the polymerization "solvent", insofar as there is a preponderance to it, and the other monomers (CM) can ideally be added in a way where the reagent is suppressed to have an optimal control of the design of the product. The UO is truly monomeric, that is, macromonomers are not present as initial material. The UO used can be products or by-products of other processes, for example, the conjugated products, thermodynamically isomerized EtHC = CHCN from monohydrocination of butadiene, EtHC = CHC02H from the hydroxycarboxylation of butadiene, EtHC = CHC02Me from carbomethoxylation of butadiene, or 2-cyanocyclooctene from the hydrocination of cyclooctadiene. Additionally, they may be esters of unsaturated fatty acids or preferably esters of unsaturated fatty acids which have been isomerized to the conjugated products. An initiator which produces carbon-centered radicals, moderate enough not to destroy the metal chelate chain transfer catalyst, is typically also used in the preparation of the polymers. Suitable initiators are azo compounds that have the requisite solubility and the appropriate half-life, and include azocumene; 2, 2'-azobis (2-methyl) -butanonitrile, 2, 2'-azobis (isobutyronitrile) (AIBN); 4, 4'-azobis (4-cyanovaleric acid); and 2- (t-butylazo) -2-cyanopropane, and other compounds known to those familiar with the art. The polymerization process, using the metal chain transfer catalysts described above, is suitably carried out at a temperature ranging from about room temperature to about 240 ° C or higher, preferably from about 50 ° C to 150 ° C. . The polymers manufactured by the process of the invention are typically prepared in a polymerization reaction by standard solution polymerization techniques, but can also be prepared by emulsion, suspension or, by volume, polymerization processes. A continuous polymerization process (CSTR) can also be used. The polymerization process can be carried out either in a batch, semilot or continuous process. When carried out in batch mode, the reactor is typically loaded with a metallic chain transfer catalyst, a conventional monomer and an unsaturated organic substance, optionally with a solvent. The desired amount of initiator is then added to the mixture, typically such that the ratio of monomer to initiator is from 5 to 1000. The mixture is then heated for a requisite time, usually about 30 minutes to about 12 hours. In a batch process, the reaction may occur under pressure to prevent monomer reflux. The unsaturated oligomers in the terminal part or the monomers prepared according to the present invention can be used, not only as non-metallic chain transfer agents, but as useful components or intermediates in the production of graft copolymers, non-aqueous dispersed polymers , microgels, star polymers, branched polymers and ladder-shaped polymers.

The oligomers, macromonomers and polymers manufactured by the present process are useful in a wide variety of coating and molding resins. Other potential uses may include cast, blown, spun or sprayed applications on fiber, film, sheet, composite materials, multiple layer coatings, photopolymerizable materials, photoprotective layers, surfactants, dispersants, adhesives, adhesion promoters, coupling agents and others. The final products take advantage of available features and may include, for example, automotive and architectural coatings or affixes that include high, solid, aqueous or solvent-based finishes. Polymers, such as those produced in this invention can find use in, for example, structured polymers for use as pigment dispersants. The freezing-pumping-reheating cycle, as used in the following examples, is described in D.F. Shriyer, et al., "The Manipulation of Air Sensitive Compounds", 2nd edition, Wiley Interscience, 1986. The spectra of ^ -RMN were taken on a QE300 NMR spectrometer (General Electric Co., Freemont, CA 94539) at a frequency 300 MHz. Mass spectroscopy K + IDS is an ionization method that produces pseudomolecular ions in the form of [M] _, with little or no fragmentation. The intact organic molecules are absorbed by rapid heating. In the gaseous phase, the organic molecules are ionized by potassium binding. Potassium ions are generated from an aluminosilicate matrix containing K20. All of these experiments were performed on a Finnegan quadrupole mass spectrometer model 4615 GC / MS (Finnegan MAT (USA), San José, CA). An electronic impact source configuration operating at 200 ° C and a pressure source of < 1 x 10"s torr PM and DP measurements were based on gene permeation chromatography (GPC) using styrene as standard, and performed on a WISP 712 chromatograph with phenogel columns 100 A, 500 A, 1000 A and 5000 A (Waters Corp., Marlborough, MA 01752-9162) .Mpic is a measure of the molecular weight of the largest molecular ion signal obtained with K + IDS and is generally a value between MN and PM.

Definitions Unless otherwise identified, all chemicals and reagents were used as received from Aldrich Chemical Co., Milwaukee, Wl. MMA = methyl methacrylate 2-PN = 2-pentenenitrile TAPCo = meso-tetra (4-methoxyphenyl) porphyrin-Co VAZO-dS ^ = 1, 1 '-azobis (cyclohexane-1-carbonitrile (DuPont Co., Wilmington, DE ) AIBN = 2, 2 '-azobis (isobutyronitrile) THPCo = tetrakis (4-hexylphenyl) porphyrin-Co DMM = dimethyl maleate EC = ethyl crotonate DEM = diethyl maleate CPO - cyclopenten-1-one PPVE = perfluoro (propylvinyl) ether EXAMPLES Example 1: Start of MMA with 2-PN A 2 mg solution of TAPCo, 2.6 mg of VAZO ^ -dd, 0.6 ml of 1,2-dichloroethane, 0.4 ml of 2-PN and 0.04 ml of MMA is degassed by three cycles of freezing-pumping-reheating, sealing and submerged in a circulation bath at 90 ° C for 2 hours. The solution is sealed and another 0.04 ml portion of MMA is added quickly. It is then degassed as described above and immersed in an isothermal bath at 90 ° C for an additional 2 hours.

The same procedure as described above is repeated at 100 ° C at 30 minute intervals, and at 110 ° C at 15 minute intervals. The K + IDS analysis shows that in all three cases, approximately 30% of a polymer product with a DP of about 3 contained only one 2-PN unit per polymer molecule. Control experiments performed as described above, but without TAPCo provide polyMMA with less than 1% 2-PN incorporated into the polymer, according to the NMR data.

Example 2: Start of MMA with 2-cyano-2-butene A 4 mg solution of TAPCo is degassed, 2 mg of AIBN, 0.7 ml of chloroform, 0.3 ml of 2-cyano-2-butene and 0.08 ml of MMA through three cycles of freezing-pumping-reheating, sealing and immersion in a circulating bath at 70 ° C for 2 hours . The solution is sealed and 0.06 ml of MMA is added quickly. It is then degassed as described above and immersed in an isothermal bath at 70 ° C for an additional 3 hours. Then another 0.06 ml of MMA is added and the solution is maintained at 70 ° C for another three hours. The K + IDS analysis shows that in all three cases, approximately 10% of a polymer product with a DP of about 3 contained only one unit of 2-cyano-2-butene per polymer molecule.

Example 3: Start of MMA with crotonaldehyde An aliquot of 0.04 ml of MMA is added to a reaction mixture which contains 5 mg of THPCo, 0.9 ml of crotonaldehyde and 8 mg of VAZO ^ -dd. The reaction solution is then degassed by three cycles of freezing-pumping-reheating, sealing and immersing in a circulating bath at 100 ° C for one hour. The above procedure is repeated twice more. According to the proton NMR of the evaporated sample under vacuum, about 60% of the polymeric product formed with a DP of about 5 contains aldehyde groups. The K + IDS analysis shows that the reaction product consists of oligoMMA and some copolymer (not separated spectrum). The control experiment is run as described above, but without THPCo, which provides polyMMA with less than 1% crotonaldehyde incorporated in the polymer, according to the NMR data.

Example 4: Start of MMA with DMM An aliquot of 0.04 ml of MMA is added to a reaction mixture which contains 5 mg of THPCo, 0.9 ml of DMM and 8 mg of VAZO ^ -Sd. The reaction solution is then degassed by three cycles of freezing-pumping-reheating, sealing and immersing in a circulating bath at 100 ° C for one hour. The above procedure is repeated twice more, but at 90 min and 150 min warm-up time. The K + IDS analysis shows that only about 15% MMA homopolymer has been formed. Approximately 50% of the remaining portion of the polymer product contains one DMM unit per molecule, and the other ~ 50% contains mainly two units of DMM. The CPG shows that DP is approximately 5.

Example 5: Start of MMA with EC An aliquot of 0.04 ml of MMA is added to a reaction mixture which contains 3 mg of THPCo, 0.9 ml of EC and 8 mg of VAZO ^ -Sd. The reaction solution is then degassed by three cycles of freezing-pumping-reheating, sealed and immersed in a circulating bath at 100 ° C for 60 min. The above procedure is repeated twice more. A product with a DP of about 4 is obtained. The K + IDS analysis shows that only about 18% MMA homopolymer has been formed. Approximately 60% of the remaining portion of the polymer product contains one unit of EC per molecule, and approximately 40% contains mainly two units of EC per molecule.

Example 6: Start of MMA with DEM An aliquot of 0.08 ml of MMA is added to a reaction mixture which contains 2 mg of THPCo, 1.8 ml of DeM and 16 mg of VAZO ^ -dd. The reaction solution is then degassed by three cycles of freezing-pumping-reheating, sealing and immersing in a circulating bath at 100 ° C for one hour. The above procedure is repeated twice more, but at 90 min and 150 min warm-up time. A product with a DP of approximately 3.5 is obtained. Analysis by K + IDS shows that only about 30% of MMA homopolymer has been formed. Approximately 70% of the remaining polymer product contains one unit of DEM per molecule, and 30% remaining contains mainly two units of DEM per molecule. The control experiment is as described above, but without THPCo, which provides polyMMA with 6% EC incorporated in the polymer, according to the NMR data.

Example 7: Start of MMA with CPO An aliquot of 0.081 ml MMA is added to a reaction mixture which contains 1 mg of bis (diphenylglyoxime) - (triphenylphosphine) cobalt (III) chloride, 1.8 ml of CPO and 16 mg of VAZO ^ -dd. The reaction solution is then degassed by three cycles of freezing-pumping-reheating, sealing and immersing in a circulating bath at 100 ° C for 40 min. The above procedure is repeated twice more, but with heating times of 90 min and 150 min. A product with a DP of about 3 is obtained. The + IDS analysis shows that approximately 50% MMA / CPO copolymer has been formed. Approximately 90% of this copolymer contains only one CPO unit per molecule.

Example 8: Copolymerization of UO An aliquot of 2.4 ml of MMA is added to a reaction mixture which contains 10 mg of THPCo, 6 ml of dichloroethane, 0.12 g of VAZO ^ -ßß, 3 ml of FREON-113 and 9 ml of PPVE. The MMA is added three times and after each addition, the reaction solution is degassed and maintained at 100 ° C for 60 minutes.

A polymer product obtained after evaporation has an Mpic = 800. According to the ICIDS analysis, 15% of polyMMA contains a molecule of PPVE. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (11)

1. An improved process for the free-radical polymerization of one or more monomers to form a polymer having end groups terminated in vinyl, the polymerization is initiated by a functional group derived from an olefinically unsaturated organic molecule, the monomers have the structure CH. = CXY wherein X is selected from the group consisting of CH3 and CH2OH; Y is selected from the group consisting of OR, 02CR, halogen, C02H, COR, C02R, CN, CONH2, CONHR, CONR2 and R '; R is selected from the group consisting of unsubstituted and substituted alkyl, substituted and unsubstituted aryl, unsubstituted and substituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, substituents being the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanate, sulfonic acid and halogen; and the number of carbons in the alkyl groups is from 1 to 12; and R 'is selected from the aromatic group consisting of unsubstituted and substituted aryl, unsubstituted and substituted heteroaryl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, amino primary, secondary amino, tertiary amino, isocyanate, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin, and halogen; the polymerization proceeds by contacting the monomers with a chain transfer agent containing cobalt and a free radical initiator at a temperature from about 25 ° to 240 ° C, wherein the monomers undergo catalytic chain transfer in the presence of the catalyst of cobalt chain transfer; the improvement is characterized in that it comprises adding an olefinically unsaturated organic molecule of the structure wherein R1 and R3 are each independently selected from the group (I) consisting of -CH (O), -CN and halogen, and of group (II) consisting of -C (0) OR5, -C (0) NRsR7, -CR8 (O), -C (0) OC (0) R9, -CiONR ^ COR11, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R1 or R3 are selected from group II, R1 and R3 can optionally form a cyclic structure; and R2 and R4 may each be independently selected from the group (III) consisting of H, -CH (O), -CN and halogen, and of group (IV) consisting of -C (0) 0Rs, -C ( 0) NR6R7, -CR8 (0), -C (O) OC (O) R9, -C (O) NR10CORl: L, -0C (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R2 or R4 are selected from group IV, R2 and R4 can optionally form a cyclic structure; R5, R6, R7, R8, R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are ^ -? ~ ?? 2; and the substituents on the alkyl or substituted aryl do not contain functionality which may substantially interfere with the free radical polymerization.

2. The process according to claim 1, characterized in that the temperature is between about 50 ° C and about 150 ° C.

3. The process according to claim 1, characterized in that the process is a batch process.

4. The process according to claim 1, characterized in that the process is semilotes.

5. The process according to claim 1, characterized in that the process is a continuous process.

6. The macromonomer, characterized in that it is produced by the process according to claim 1.

7. A macromonomer, characterized in that it is constituted of the structure characterized in that m varies from 1 to 100; wherein R1, R2, R3 and R4 can each be independently selected from the group consisting of H, -CH (O), -CN, halogen, -C (0) ORs, -C (0) NReR7, -CR8 ( O), -C (O) OC (O) R9, -C (O) NR10COR1: L, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; R1 and R3 or R2 and R4 can be combined in a cyclic structure when R1, R2, R3 or R4 are -C (0) ORs, -C (0) NR6R7, -CR8 (0), -C (O) OC ( O) R9, -C (O) NR10COR1: L, -0C (0) R12, -OR13, alkyl, substituted alkyl, aryl or substituted aryl; and with the additional proviso that at most two of R1, R2, R3 and R4 can be H; R5, R6, R7, R8, R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R1 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are C1-2 and the substituents on the alkyl or substituted aryl do not contain functionality which may substantially interfere with the free radical polymerization; and wherein Y is selected from the group consisting of OR, 02CR, halogen, C02H, COR, C02R, CN, CONH2, CONHR, CONR2 and R '; R is selected from the group consisting of unsubstituted and substituted alkyl, substituted and unsubstituted aryl, unsubstituted and substituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, substituents being the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanate, sulfonic acid and halogen; and the number of carbons in the alkyl groups is from 1 to 12; and R 'is selected from the aromatic group consisting of unsubstituted and substituted aryl, substituted and unsubstituted heteroaryl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, amino primary, secondary amino, tertiary amino, isocyanate, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin, and halogen.

8. The macromonomer according to claim 7, characterized in that R1 and R2 are not H at the same time.

9. An improved process for free radical polymerization of one or more monomers to form a polymer having end groups terminated in vinyl, the polymerization is initiated by a functional group derived from an olefinically unsaturated organic molecule, the monomers have the structure CH2 = CXY wherein X is selected from the group consisting of CH3 and CH20H; Y is selected from the group consisting of OR, 02CR, halogen, C02H, COR, COzR, CN, C0NH2, CONHR, C0NR2 and R '; R is selected from the group consisting of unsubstituted and substituted alkyl, substituted and unsubstituted aryl, unsubstituted and substituted heteroaryl, substituted and unsubstituted aralkyl, substituted and unsubstituted alkaryl, and substituted and unsubstituted organosilyl, substituents being the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino, secondary amino, tertiary amino, isocyanate, sulfonic acid and halogen; and the number of carbons in the alkyl groups is from 1 to 12; and R1 is selected from the aromatic group consisting of unsubstituted and substituted aryl, substituted and unsubstituted heteroaryl, the substituents are the same or different and are selected from the group consisting of carboxylic acid, carboxylic ester, epoxy, hydroxyl, alkoxy, primary amino , secondary amino, tertiary amino, isocyanate, sulfonic acid, substituted and unsubstituted alkyl, substituted and unsubstituted aryl, substituted and unsubstituted olefin, and halogen; the polymerization proceeds by contacting the monomers with a chain transfer agent containing cobalt and a free radical initiator at a temperature from about 25 ° to 240 ° C, wherein the monomers undergo catalytic chain transfer in the presence of a catalyst of cobalt chain transfer; the improvement is characterized in that it comprises adding an olefinically unsaturated organic molecule of the structure wherein R1 and R2 are hydrogen, and R3 and R4 are each independently selected from the group (I) consisting of -CH (O), -CN and halogen, and of group (II) consisting of -C (0) ORs, -C (0) NR6R7, -CR8 (0), -C (0) OC (0) R9, -C (O) NR ^ COR11, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and substituted aryl; wherein, when R3 or R4 are selected from group II, R3 and R4 optionally can form a cyclic structure; or wherein R3 and R4 may each be independently selected from the group (III) consisting of H, -CH (0), -CN and halogen, and of group (IV) consisting of -C (0) 0R5, - C (0) NRsR7, -CR8 (0), -C (O) OC (O) R9, -C (O) NR ^ COR11, -OC (0) R12, -OR13, alkyl, substituted alkyl, aryl and aryl replaced; wherein, R3 or R4 are selected from group IV, R3 and R4 optionally can form a cyclic structure; R5, R6, R7, R8, R9, R10, R11 and R12 are H, alkyl, aryl, substituted alkyl or substituted aryl; R 13 is alkyl, aryl, substituted alkyl or substituted aryl; wherein the alkyl and the substituted alkyl are c? -C_2, and the substituents on the alkyl or substituted aryl do not contain functionality which can substantially interfere with the free radical polymerization.

10. The process according to claim 9, characterized in that the temperature is between about 50 ° C and about 150 ° C.

11. The process according to claim 9, characterized in that the process is carried out in a process configuration that is selected from the group consisting of a batch process, a continuous process or a semilot process.