MXPA00001732A - Functionalized diene oligomers - Google Patents

Abstract

This invention relates to the controlled molecular weight production of macromonomers and polymers with terminal conjugated double bonds from starting monomers including, but not limited to, substituted butadienes. The terminal diene end thus produced is also a potential reaction site for further polymerization or functionalization. The molecular weight is controlled by use of Co chain transfer catalysts and appropriate process conditions.

Description

DIENO OLIGOMEROS FUNCIONALIZADOS FIELD OF THE INVENTION This invention relates to the controlled molecular weight production of macromonomers and polymers with terminal conjugated double bonds from starting monomers including, but not limited to substituted butadienes. The terminal diene end of this produced form is also a potential reaction site for further polymerization or functionalization.

TECHNICAL BACKGROUND It is well known in the production of chloroprene and poly (chloroprene) for those skilled in the art. U.S. Patent No. 5,357,010 discloses a process for producing poly (chloroprene) with a plurality of monomer units terminated by ~ S-alkyl xanthogen and / or ~ S-acylaminophenyl groups. All the chain transfer agents used therein contain sulfur. U.S. Patent No. 3,775,390 describes the polymerization of chloroprene in a REF .: 32295 alkaline aqueous emulsion in the presence of both chain transfer agents containing organic sulfur and a benzothiozolsulfenamide. U.S. Patent No. 4,742,137 describes a process for producing an aqueous dispersion of polymer particles comprised of a conjugated diene and crystalline polymer. Two catalysts are used, but none are the Co complexes used in the present invention. U.S. Patent No. 4,694,054 describes the use of cobalt chain transfer catalysts for molecular weight control and production of macromonomers. U.S. Patents Nos. 5,231,131 and 5,362,826 describe the incorporation of methacrylate oligomers obtained by the cobalt-catalyzed chain transfer reaction in a polymer backbone by copolymerization with another or the same monomers to form copolymers of different architecture ( graft, block copolymers, branched, etc.). U.S. Patent No. 5,587,431 describes a method for preparing terminally unsaturated polymer compositions by re-terminating the termini of an oligomer terminally unsaturated with additional chain transfer catalyst (CTC) for additional oligoing. The co-pending application Serial No. (applicant's file number FA-0741), filed on February 18, 1997, describes the molecular weight control of acrylates and styrenics using cobalt chain transfer catalysts. A reaction catalyzed by palladium of 1,1-dichloroethylene with acetylenes and vinylalanols has been reported to produce chlorinated products having conjugated double bonds. (See Tetrahedron Letters, 28 (15), pp. 1649-1650, 1987). However, the products are not polymeric in nature. The polymers with pentadiene functionality at the chain end can be produced using addition fragmentation chain transfer agents which are derived from conjugated dienes. These chain transfer agents generally include sulfur compounds. See generally Prog. Polym. Sci., 21, 1996, pp. 439-503. Polym. Preprints 38 (1), 1997, pp. 663-664 and 746-747, and J. Polym. Sci., Part A: Polym. Chem. 33 (16), 1995, 2773-86. The resulting polymers have differentiable structures from those claimed herein.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a process for polymerizing substituted butadienes to substituted polybutadienes having controlled molecular weight and end group functionality, the process employing a cobalt chain transfer catalyst in the presence of a free radical initiator. A process for polymerizing substituted butadienes to substituted polybutadienes having controlled molecular weight and end group functionality is described; wherein the process consists in contacting a substituted butadiene, in the optional presence of a comonomer, with a cobalt chain transfer catalyst and a free radical initiator, the substituted butadienes have a structure CHRa = CX-CY = CR2CR3 where X and Y are independently each selected from the group consisting of H, alkyl, substituted alkyl, C00 (Metal), COOR, CN, OR, -COR, -C0NR2, -OCOR, halogen, aryl, and substituted aryl; where R is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, and hydrogen; the alkyl and the substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms; and with the proviso that both X and Y are not both H; wherein the metal is selected from the group consisting of lithium, sodium, potassium, magnesium, cadmium and zinc; wherein R1, R2 and R3 are each selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN and hydrogen; the alkyl and the substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms; and wherein any two of R1, R2 and R3 are optionally arranged in a cyclic structure; the reaction is carried out at a temperature from about room temperature to about 240 ° C, in the optional presence of a solvent. This invention also relates to the polymer or terminally functionalized oligomers resulting from the structure: R2R3C__CY I (CHR1-CX-CY-CR2R3) n- (CHRi-CX) m-CRi = CX-CY »= CR2R3 wherein I is an initiating group derived from an initiator for the polymerization process, or a hydrogen atom derived from the cobalt chain transfer catalyst; n is greater than 2; m is zero or greater; and wherein R1, R2 and R3 are selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN and hydrogen; the alkyl and the substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms.

DETAILS OF THE INVENTION The polymerization of substituted butadienes involves the use of a cobalt chain transfer catalyst in the presence of an initiator, and can be run in any generally used batch and continuous polymerization mode (CSTR). The methods employed in this invention are described below. By "controlled molecular weight" is meant a substantially lower molecular weight than that which can be obtained in the absence of the chain transfer catalyst. Typically, the molecular weights may be less than half that are obtained without the chain transfer catalyst and preferably less than 25% that are obtained without the chain transfer catalyst. Preferred substituted dienes include chloroprene, isoprene, 2-phenyl-1,3-butadiene, cyanopene, 2-carbomethoxy-l, 3-butadiene and 2,3-dichloro-l, 3-butadiene. The most preferred substituted dienes are chloroprene and 2,3-dichloro-1,3-butadiene.

Preferred metal chain transfer catalysts for use in the manufacture of the materials present 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 on 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 described respectively in Eniolopov, N.S., et al., USSR Patent 664,434 (1978); Golikov, I., et al., USSR Patent 856,096 (1979); Belgovskii, I.M., USSR Patent 871,378 (1979); Y Belgovskii, I.M., et al., USSR Patent 1,306,085 (1986). These catalysts operate close to the controlled proportions of diffusion and are effective in concentrations of parts per million. 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 C? (II) (DMG-BF2) 2 J = K = Me, L = ligand C? (II) (EMG-BF2) 2 J = Me, K = Et, L = ligand C? (II) (DEG-BF2) 2 J = K = Et, L = ligand C? (II) (CHG-BF2) 2 J = K = - (CH2) 4-, L = ligand QC? (III) (DPG-BF2) 2 J = K = Ph, R = alkyl, L = ligand QCo (III) (DMG-BF2) 2 J = K = Me, R = alkyl, L = ligand QCo (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 QC? (III) (DMG-BF2) 2 J = K = Me, R = halogen, L = ligand L may be a variety of additional neutral ligands commonly known in coordination chemistry. Examples include water, amines, ammonia and phosphines. The catalysts can also include cobalt complexes of a variety of porphyrin molecules such as tetraphenylporphyrin, tetraanisylporphyrin, tetramesitylporphyrin and other substituted species. Q is an organic radical (eg, alkyl or substituted alkyl); Preferred Q groups are isopropyl, 1-cyanoethyl, and 1-carbomethoxyethyl. The catalyst used in the following examples is commonly known as COBF, which represents the chemical name (Bis- [(1,2-dimethyl-ethanedioximate) (2-) 0: 0 '-tetrafluorodiborate (2-) -N'N " N '"N" "] (2-propyl) cobalt (III)). It is one of the most active catalysts. Chloroprene is preferred for self-polymerization (see generally Kirk-Or Encyclopedia of Chemical Technology, Vol. 8, pp. 515-534, John Wiley &Sons, 979). However, the presence of terminal conjugated double bonds, as found in the present invention, allows the copolymerization of chloroprene at an improved ratio. Chloroprene, isoprene, 2-phenyl-1,3-butadiene and other related diene monomers they can be copolymerized with one or more acrylates, methacrylates, styrenes, acrylonitrile, methacrylonitrile, or related vinyl compounds capable of copolymerization of free radicals with chloroprene. Preferred comonomers are: acrylonitrile, methacrylonitrile, vinylmethyl ketone, 4-chloroestene, 4-chloromethyl tyrolenes, 2,3-dimethylenes, 3,4-dichlorostyrene, 4-bromostyrene, 4-hydroxystyrene, 4-methoxyes, 5-methoxymethyl, thyroxin, 4-bromomethyl-styrene, 4-styrenesulfonic acid, sodium salt of 4-is-tynesulfonic acid, 4-styrene-sulfonyl chloride, methyl acrylate, ethyl acrylate, propyl acrylate, 2-hydroxyethyl acrylate, acrylate of 3-hydroxypropyl, 2-hydroxypropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, dodecyl acrylate, glycidyl acrylate, acrylamide, N, N'-dimethylacrylamide, bis-acrylamide, 2-acrylamido-2-methyl-1-propanesulonic acid, acrylic acid, sodium salt of acrylic acid, zinc salt of acrylic acid, acryloyl chloride, [2- (acryloyloxy) ethyl] tri chloride ethylammonium, 2-ethyloxyethyl acrylate, 2- (N, N'-dimethyl) acrylate ino) -ethyl, methacryloyl chloride, methacrylic anhydride, acrylic anhydride, [2- (methacryloyloxy) ethyl] - trimethylammonium, 2- (methacryloyloxy) ethyl methacrylate, 2- (methacryloyloxy) ethyl acetoacetate, [2- (methacryloyloxy) 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, alpha methylstyrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate methacrylate, dimethoxymethyl-silylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxy etilsililpropilo methacrylate diisopropoximetilsililpropilo methacrylate etoxisililpropilo di methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl butyrate, isopropenyl acetate, isopropenyl benzoate, isopropenyl chloride of isopropenyl, isopropenyl fluoride, isopropenyl bromide, itaconic acid, itaconic anhydride, dimethyl itaconate, methyl itaconate, N-tert-butyl methacrylamide, Nn-butyl methacrylamide, N- methyl-ol-methacrylamide, N-ethyl-ol-methacrylamide, isopropenylbenzoic acid (all isomers), diethylamino-alpha-methylstyrene (all isomers), para-methyl-alpha-methylstyrene (all isomers), diisopropenylbenzene (all isomers), isopropenylbenzenesulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, ethyl 2-hydroxymethylacrylate, propyl 2-hydroxymethylacrylate (all isomers), butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate, isobornyl 2-hydroxymethylacrylate, methyl-chloromethyl acrylate, ethyl 2-chloromethylacrylate, propyl 2-chloromethylacrylate (all isomers), butyl 2-chloromethyl acrylate (all isomers), 2-ethylhexyl 2-chloromethylacrylate, isobornyl 2-chloroethylacrylate and vinylpyrrolidone. An initiator that produces carbon-centered radicals, soft enough not to destroy the metal chelate chain transfer catalyst, is also typically employed in preparing the polymers. Suitable initiators are azo compounds that have the necessary solubility and appropriate half-life, including azocumene; 2, 2'-azobis (2-methyl) -butanonitrile; 2, 2'-azobis (isobutyronitrile) (AIBN); 4, 4'-azobis (4-cyanovaleric acid); and 2- (t-butylazo) -2-cyanopropane.

The polymerization process, employing the metal chain transfer catalysts described above, is suitably performed at a temperature ranging from about room temperature to about 240 ° C or higher, preferably from about 50 ° C to 150 ° C. The polymers made by the inventive process are typically prepared in a polymerization reaction by standard solution polymerization techniques, but can also be prepared by emulsion, suspension or bulk polymerization processes. The polymerization process can be carried out either as a batch, semi-batch or continuous process (CSTR). When performed in the batch mode, the reactor is typically charged with the metal chain transfer catalyst, and the monomer or monomers selected, optionally with a solvent. The desired amount of initiator is then added to the mixture, typically such that the monomer to initiator ratio is from 5 to 1000. The mixture is then heated for the necessary time, usually from about 30 minutes to about 12 hours. In a batch process, the reaction can be run under pressure to prevent reflux of the monomer.

The polymerization can be carried out in the absence of a solvent or in the presence of any suitable solvent or medium for polymerization of free radicals, including, but not limited to, ketones such as acetone, butanone, pentanone and hexane, alcohols such as isopropanol, amides. such as dimethylformamide, aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran, diethyl ether and ethylene glycol, dialkyl ethers such as the solvent Cellosolves ™, mixed alkyl ethers or ester ethers such as onoalkylether-onoalkanoates, and mixtures of two or more solvents. The freeze-pump-thaw cycle, as used in the subsequent examples, is described in D.F. Shriver, et al., "The Manipulation of Air Sensitive Compounds." 2nd ed., Wiley Interscience, 1986. A key advantage of the present invention is to avoid sulfur-containing catalysts. These sulfur compounds have unpleasant odors, and produce byproducts of waste that must then be thrown away, thus impacting the environment. This invention produces relatively clear products that need little additional purification, and therefore can reduce the cost of the final products. Relatively clear materials can be used for "0" rings, adhesives, in coatings and paints, as well as any other products in which poly (chloroprene) is commonly used. The oligomers, macromonomers and polymers made by the present process are useful in a wide variety of molding and coating resins. Other potential uses may include molding, blowing, rubbing or spraying applications on fiber, film, sheets, composite materials, multi-layer coatings, light-cured materials, photoresists, surfactants, dispersants, adhesives, adhesion promoters, coupling agents, and others. The terminally unsaturated oligomers or macromonomers prepared according to the present invention can be employed, not only as non-metallic chain transfer agents, but as useful or intermediate components in the produn of graft copolymers, non-aqueous dispersed polymers, raicrogels, polymers star, branched polymers, and ladder polymers. Terminal products that take advantage of available features may include, for example, example, automotive and architectural coatings or finishes, including elevated, aqueous, or solvent-based finishes. Poly (chloroprene) in particular finds use in articles such as adhesives and "O" rings, and in electrical insulation, conveyor belts and protective clothing when vulcanized. The product of the reaction is a terminally functionalized polymer or oligomer of the structure R2R3C < = CY I (CHR ^ -CX-CY-CR ^ 3 ^ - (CHR1-CX) m-CR1-CX-CY = CR2R3 wherein I is an initiating group derived from an initiator for the polymerization process, or a hydrogen atom derived from the cobalt chain transfer catalyst; n is greater than 2; m is zero or greater; and wherein R1, R2, and R3 are selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN, and hydrogen; the alkyl and substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms. The preferred product of the reaction with chloroprene is a terminally functionalized polymer or oligomer of the structure I-. { CH2-CCl-CH-CH2) where n is greater than 2; and m is zero or greater. The preferred product of the reaction with 2,3-chloro-1,3-butadiene is a terminally functionalized polymer or oligomer of the structure I- (CH2-CCl »CCl-CH2) where n is greater than 2; and m is zero or greater. The preferred product of the reaction of the chloroprene product with maleic anhydride is a polymer or terminally functionalized oligomer of the structure where n is greater than 2; and m is zero or greater. The presence of terminal conjugated double bonds in the products made by this process is shown in two forms. The 1HMR clearly shows resonances in the 6.2-6.6 ppm region in all the polychloroprenes obtained with the cobalt catalyst. Experimentation with model compounds and a two-dimensional NMR spectrum proves that only the protons of the following structure = C (C1) -CH =, can have such signals. The comparison of the Mn obtained by GPC correlate well with those obtained from the NMR data considering signals of 6.2-6.6 ppm that come from a single proton of the end group. Also, it is known to those skilled in the art that conjugated dienes react with maleic anhydride in a very specific manner different from that of non-conjugated di- and polyenes. This reaction is the reaction of Diels-Alder (J. March, Advanced Organic Chemistry, Wiley: N.Y., 1992, p.839). The catalytic chain transfer of this invention generates a pair of conjugated double bonds at the end or each polymeric or oligomeric chain. The presence of this active end group allows further functionalization of the resulting oligomer by functional dieneophiles such as anhydrides (e.g., maleic anhydride), nitriles (e.g., fumaronitrile or tetracyanoethylene), and amides (e.g., ethyl maleamide) through the reactions of Diels-Alder. The Diels-Alder reaction is successfully conducted with the terminally functionalized polychloroprenes of this invention with maleic anhydride as a dienophile (Example 8). Therefore, this reaction proves that the end groups = C (C1) -CH = are present and that this group is as reactive as the conjugated diene in its monomeric analogs. The presence of the terminal conjugate double bond allows further modification of the chloroprene oligomers by grafting these oligomers onto other polymers, radical copolymerization with other monomers, synthesis of pigment dispersants and compatibilizers, production of reactive thermosetting material, and the like. The NMR-1 spectra are taken !! in a QE300 NMR spectrometer (General Electric Co., Free ont, CA 94539) at a frequency of 300 MHz. Mass spectroscopy K + IDS is an ionization method that produces pseudomolecular ions in the form of [M] K + with little or no fragmentation. The intact organic molecules are desorbed by rapid heating. In the gas phase, the organic molecules are ionized by potassium binding. Potassium ions are generated from an aluminosilicate matrix containing K20. All these experiments are performed on a Finnegan quadripole mass spectrometer Model 4615 GC / MS (Finnegan MAT (USA), San José, CA). An electron impact source configuration operating at 200 ° C and a source pressure of <is usedlxl0 ~ 6 torr. MALDI MS (matrix-assisted laser desorption / ionization mass spectroscopy) is performed on a VisionMR 2000 instrument (Thermo Bioanalysis Ltd., Paradise, Hemel Hempstead Herts., HP2 4TG, UK), generally following the technique described by G. Montaudo, et al., In Macromolecules, 28 (1995), pp. 7983-89.0.

The MW and DP measurements are based on gel permeation chromatography (GPC) using styrene as a standard, and performed on a WISP 712 Chromatograph with 100 A, 500 A, 1000 A and 5000 A phenogel columns (Waters Corp ., Marlborough, MA 01752-9162).

Definitions Unless otherwise specified, all chemicals and reagents are used as received from Aldrich Chemical Co. , Mil aukee, Wl. The following abbreviations have been used and are defined as: VAZOMR, -52 = 2, 2'-azobis (2,4-dimethylvaleronitrile) (DuPont Co., Wilmington, DE) VAZOMR, -88 = 1, 1 '-azobis ( cyclohexane-1-carbonitrile (DuPont Co., Wilmington, DE) AIBN = 2, 2'-azobisisobutyronitrile Neoprene ™, = synthetic polychloroprene rubber (DuPont Co., Wilmington, DE) DP = polymerization degree Mn is average number-average molecular weight Mw is weight average molecular weight THF is tetrahydrofuran EXAMPLES General Procedure The polymerization of chloroprene (2-chloro-1,3-butadiene) in solution as well as in the bulk monomer is conducted at temperatures between 50 ° C and 90 ° C. The process temperature is determined by the azo-initiator used. Any chain transfer catalyst can be used in the process; the examples herein are made using mainly COBF which is one of the most active chain transfer catalysts. Other catalysts are also used but with relatively lower efficiency. The polymer formed from the reaction mixture is isolated by evaporation, but can also be isolated by precipitation or any other method known to those skilled in the art. As shown below, the reaction can be done with a "pure" monomer or with a solvent (1,2-dichloroethane) to achieve the desired end product.

EXAMPLE 1 A reaction mixture containing 0.3 g of COBF, 0.8 g of VAZOMR-52, 30 ml of 2-chloro-1,3-butadiene and 60 ml of 1,2-dichloroethane is degassed for three cycles of pump-freezing -freezing and it place in an oil bath at 60 ° C. After 20 hours, evaporate in vacuo to remove the solvent and the unreacted monomer to give 24 g of a waxy polymer. The GPC analysis shows that the polymer product has an average polymerization degree number (Mn) of 1741 and a Polydispersity Index of 3.15.

EXAMPLE 2 A reaction mixture containing 20 mg of bis- (diphenylglyoximate) (triphenylphosphino) (chloride) Co (III), 56 mg of VAZOMR-52, 52 and 8 ml of 2-chloro-l, 3-butadiene is degassed. for three freeze-pump-thaw cycles and placed in an oil bath at 60 ° C. After 4 hours the reaction mixture is evaporated in a vacuum to give 6.1 g of a rubber polymer. The GPC analysis shows that the polymer product has Mn = 59200 and a Polydispersity Index of 2.4.

EXAMPLE 3 A reaction mixture containing 200 mg of COBF, 0.35 g of VAZOMR-88, 20 ml of 2-chloro-l, 3-butadiene and 40 ml of 1,2-dichloroethane for three freeze-pump-thaw cycles and place in an oil bath at 90 ° C. After 4 hours the reaction mixture is evaporated in a vacuum to give 12 g of viscous polymer. The GPC analysis shows that the polymer product has an Mn = 471 and a Polydispersity Index of 1.77.

EXAMPLE 4 A reaction mixture containing 6 mg of COBF, 20 mg of AIBN, 3 ml of 2-chloro-1,3-butadiene and 0.09 ml of methacrylic acid is degassed by three freeze-pump-thaw cycles and placed in an oil bath at 70 ° C. After 2 hours the reaction mixture is evaporated in a vacuum to give 0.6 g of a waxy polymer. The GPC analysis shows that the polymer product has Mn = 12100 and a Polydispersity Index of 1.85.

EXAMPLE 5 A reaction mixture containing 2 mg of COBF, 4 mg of VAZOMR-88, 1.5 ml of 2-chloro-1,3-butadiene, 0.5 ml of 1,1-vinylidene chloride and 2 ml of 1 is degassed. , 2-dichloroethane for three freeze-pump-thaw cycles and placed in an oil bath at 90 ° C. After 3 hours the reaction mixture is evaporated under high vacuum to give 0.4 g of a waxy polymer. The K + IDS analysis shows that more than 70% of the entire polymer chain contains the vinylidene units, Mn = 720. The proton NMR shows the characteristic of doublet resonance of doublets at 6.25 ppm.

EXAMPLE 6 A reaction mixture containing 2 mg of COBF, 4 mg of VAZOMR-88, 1.8 ml of 2-chloro-1,3-butadiene, 0.2 ml of methacrylic acid and 2 ml of 1,2-dichloroethane is degassed. three freeze-pump-thaw cycles and place in an oil bath at 90 ° C. After 3 hours the reaction mixture is evaporated under high vacuum to give 0.5 g of a waxy polymer. The K + IDS analysis shows that more than 85% of the entire polymer chain contains the acrylic acid units, Mn was approximately 500 (bimodal molecular weight distribution). The proton NMR shows several doubles of doublet resonance at 6.1-6.3 ppm.

EXAMPLE 7 A reaction mixture containing 12 mg of COBF, 25 mg of AIBN, 2 ml of 50% xylene solution of 2,3-dichloro-l, 3-butadiene and 2 ml is degassed. of 1,2-dichloromethane for three freeze-pump-thaw cycles and placed in an oil bath at 70 ° C. After 6 hours the reaction mixture is evaporated under high vacuum to give 0.6 g of a white polymer. The polymer is partially soluble in methylene chloride. The GPC analysis of the soluble part gives Mn = 5240. The carbon and proton NMR indicates the presence of the fragments Rn-CC1 = CC1 = CH2 in the obtained polymer.

EXAMPLE 8 The oligocloroprene obtained in Example 3 (1.2 g) is mixed with 0.25 g solution of maleic anhydride recently sublimated in 3 ml of tetrahydrofuran. The solution obtained is maintained 12 hours at 70 ° C under nitrogen. After evaporation in vacuo at room temperature, the residual polymer is analyzed by MALDI mass spectrometry. The comparison of the MALDI spectra of the oligocloroprene before heating with maleic anhydride and after heating indicates that in the second case only one unit of maleic anhydride per polymer chain is incorporated. The NMR spectrum shows the disappearance of some vinyl protons (6.1-6.5 ppm) with simultaneous formation of new characteristic resonances for the Diels-Alder product as model experiments with indicated monomeric chloroprene and maleic anhydride.

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.

Claims (10)

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

1. A process for polymerizing substituted butadienes to substituted polybutadienes having controlled molecular weight and end group functionality; characterized in that the process consists of: contacting a substituted butadiene, in the optional presence of a comonomer, with a cobalt chain transfer catalyst and a free radical initiator, the substituted butadienes have a structure CHR1 = CX-CY = CR2CR3 wherein X and Y are independently each selected from the group consisting of H, alkyl, substituted alkyl, COO (Metal), -COOR, CN, OR, -COR, -CONR2, -OCOR, halogen, aryl, and substituted aryl; where R is selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, and hydrogen; the alkyl and the substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms; and with the proviso that both X and Y are not both H; wherein the metal is selected from the group consisting of lithium, sodium, potassium, magnesium, cadmium and zinc; wherein R1, R2 and R3 are each selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN and hydrogen; the alkyl and the substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms; and wherein any two of R1, R2 and R3 are optionally arranged in a cyclic structure; the reaction is carried out at a temperature of about room temperature at about 240 ° C, in the optional presence of a solvent.

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

3. The process according to claim 1, characterized in that the substituted butadiene is selected from the group consisting of chloroprene, isoprene, 2-phenyl-1,3-butadiene, cyanoprene, 2-carbomethoxy-1,3-butadiene, and 2, 3-dichloro-l, 3-butadiene.

4. The process according to claim 2, characterized in that the substituted dienes are chloroprene or 2,3-dichloro-l, 3-butadiene.

5. The process according to claim 4, characterized in that the metal chain transfer catalyst is selected from the group consisting of cobalt (II) and (III) chelates or a mixture thereof.

6. The process according to claim 5, characterized in that a comonomer is used and the comonomer is selected from the group consisting of acrylonitrile, methacrylonitrile, vinyl methyl ketone, 4-chloro tyno, 4-chloromethyl tyno, 2,3-dimethylstyrene, 3, 4-dichlorostyrene, 4-bromo-styrene, 4-hydroxystyrene, 4-methoxystyrene, 4-oxymethylstyrene, 4-bromomethyl-styrene, 4-styrenesulfonic acid, sodium salt of 4-styrenesulfonic acid, 4-styrene chloride sulfonyl, methyl acrylate, ethyl acrylate, propyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, dodecyl acrylate, glycidyl acrylate, acrylamide, N, N'-dimethylacrylamide, bis-acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylic acid, sodium salt of acrylic acid, salt of zinc acrylic acid, acryl chloride ilo, [2- (acryloyloxy) ethyl] trimethylammonium chloride, 2-ethyloxyethyl acrylate, 2- (N, N'-dimethylamino) -ethyl acrylate, methacryloyl chloride, methacrylic anhydride, acrylic anhydride, [2- (methacryloyloxy) ethyl] -trimethylammonium, 2- (methacryloyloxy) ethyl methacrylate, 2- (methacryloyloxy) ethyl acetoacetate, chloride [2- (methacryloyloxy) 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, alpha methylstyrene, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate methacrylate, dimethoxymethyl-silylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate dibutoximetilsililpropilo methacrylate diisopropoximetilsililpropilo methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl butyrate, isopropenyl acetate, isopropenyl benzoate, isopropenyl, isopropenyl chloride , isopropenyl bromide, isopropenyl bromide, itaconic acid, itaconic anhydride, dimethyl itaconate, methyl itaconate, N-tert-butyl methacrylamide, Nn-butyl methacrylamide, N-methyl-ol-methacrylamide, N-ethyl-ol-methacrylamide, acid isopropenylbenzoic acid (all isomers), diethylamino-alpha-methylstyrene (all isomers), para-methyl-alpha-ethylstyrene (all isomers), diisopropenylbenzene (all isomers), isopropenylbenzenesulfonic acid (all isomers), methyl 2-hydroxymethylacrylate, ethyl 2-hydroxymethylacrylate, Propyl 2-hydroxymethyl methacrylate (all isomers), butyl 2-hydroxymethylacrylate (all isomers), 2-ethylhexyl 2-hydroxymethylacrylate, isobornyl 2-hydroxymethylacrylate, methyl 2-chloromethyl acrylate, ethyl 2-chloromethyl acrylate, 2-chloromethylacrylate of propyl (all isomers), butyl 2-chloromethylacrylate (all isomers), 2-ethylhexyl 2-chloromethyl acrylate, isobornyl 2-chloromethylacrylate and vinylpyrrolidone.

7. A terminally functionalized oligomer or polymer having the structure: R2R3OCY I (CHR1-CX-CY-CR2R3) n- (CHR1-CX5m-CR: -CX-CY '= CR2R3 characterized in that I is an initiation group derived from an initiator for the polymerization process, or a hydrogen atom derived from the cobalt chain transfer catalyst; n is greater than 2; m is zero or greater; and wherein R1, R2 and R3 are selected from the group consisting of alkyl, substituted alkyl, aryl, substituted aryl, halide, nitrile, ester, ether, CN and hydrogen; the alkyl and the substituted alkyl groups have one or more carbon atoms; the aryl groups have six or more carbon atoms.

8. The process according to claim 1, characterized in that the initiator is an azo compound.

9. The process according to claim 8, characterized in that the initiator is selected from the group consisting of azocumene; 2,2'-azobis (2-methyl) -butanonitrile; 2,2 '-azobis (isobutyronitrile) (AIBN); 4, 4'-azobis (4-cyanovaleric acid); and 2- (t-butylazo) -2-cyanopropane.

10. The process according to claim 1, characterized in that it is conducted in the presence of a solvent selected from the group consisting of ketones, alcohols, amides, aromatic hydrocarbons, ethers, dialkyl ethers, alkylesters, mixed ester ethers and mixtures of two or more of the solvents. DIENO OLIGOMEROS FUNCIONALIZADOS SUMMARY OF THE INVENTION This invention relates to the controlled molecular weight production of macromonomers and polymers with terminal conjugated double bonds from starting monomers including, but not limited to, substituted butadienes. The terminal diene end produced in this way is also a potential reaction site for further polymerization or functionalization. Molecular weight is controlled by the use of Co chain transfer catalysts and appropriate process conditions.