WO2018150061A1 - Vinylic addition polynorbornenes with trispyrazolylborate groups - Google Patents

Vinylic addition polynorbornenes with trispyrazolylborate groups Download PDF

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WO2018150061A1
WO2018150061A1 PCT/ES2017/070839 ES2017070839W WO2018150061A1 WO 2018150061 A1 WO2018150061 A1 WO 2018150061A1 ES 2017070839 W ES2017070839 W ES 2017070839W WO 2018150061 A1 WO2018150061 A1 WO 2018150061A1
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formula
vinyl
polynorbornene
groups
hydrocarbyl
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PCT/ES2017/070839
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Spanish (es)
French (fr)
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Ana Carmen ALBÉNIZ JIMÉNEZ
Jesús Ángel MOLINA DE LA TORRE
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Universidad De Valladolid
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides

Definitions

  • the present invention is within the field of polymerization functionalization.
  • it constitutes an advance in the synthesis of polymers with ligands capable of coordinating metals that give rise to materials with properties of interest to the industry or, if the metals have catalytic activity, which can be used as catalyst support.
  • the polymers described herein contain in their structure tridentate trispyrazolylborate type ligands. These ligands make it possible to carry out catalysis reactions successfully and, their introduction into the structure of the vinyl addition polynorbornene described herein results in polymers that can be used to obtain recoverable and recyclable catalysts.
  • scorpionate ligands are an important class of polydentate ligands that coordinate metals very effectively, generally occupying three adjacent coordination positions.
  • the activity and selectivity of the catalysts containing trispyrazolylborate type ligands, RBpz 3 " can be modulated simply by varying the nature of the R group and, above all, the substituents in the pyrazole fragment that lead to trispyrazolylborates with different electronic and size characteristics.
  • the possibility of having a wide family of ligands that allow a fine adjustment of the characteristics of the metal complexes is an important advantage of these derivatives.
  • one of the main challenges of synthetic chemistry is to achieve sustainable processes for the construction of molecules. For this, it is essential, among other aspects, to obtain more active and selective catalysts, as well as to avoid the generation of waste after the reactions.
  • One of the strategies to achieve this objective is the use of catalysts supported on a solid, so that they can be easily separated from the desired products and, additionally, can be reused. When recycling the catalyst, this process avoids discarding it after each reaction and allows, in fact, to increase its activity since the total number of catalytic cycles that it provides during its useful life can become very high.
  • the present invention provides new functionalized polymers of formula (I), where trispyrazolylborate type ligands are anchored to the structure of vinyl polynorbornenes. These polymers are capable of withstanding both mild and more demanding reaction conditions. In this way, the new polymeric compound can coordinate metals with catalytic activity and, after the reaction, the polymer can be filtered off the desired product and reused.
  • the vinyl addition polynorbornene has a completely aliphatic polycyclic skeleton, which has demonstrated remarkable stability as a support in other catalytic processes in which it has been used.
  • stanyl vinyl addition polynorbornenes are recyclable reagents in Stille coupling reactions catalyzed by palladium
  • polymer of formula (I) described in this patent application can be obtained by simple synthesis, and the pyrazole groups present in the Pol-Bpz 3 ⁇ ligand can be any pyrazole, with or without substituents. This versatility is a great advantage for later application.
  • Another additional advantage of the polymer of formula (I) is that the bond between the -Bpz 3 group and the vinyl polynorbornene takes place by an alkyl chain, more flexible than the previously used aryl anchors.
  • the present invention provides a compound belonging to a new family of vinyl addition polynorbornenes with trispyrazolylborate groups.
  • the present invention relates to a vinyl polynorbornene of formula (I)
  • R 1 , R 2 and R 3 are the same or different monovalent groups
  • R 4 is hydrogen or hydrocarbyl
  • M is a monovalent metal
  • m takes values between 25 and 200;
  • n takes integer values between 0 and 18;
  • the ratio x / y takes values between 30 and 0.
  • m is a variable value depending on the molecular weight distribution of the different initial polymers (Mw, Mn and the relationship between these values or polydispersity).
  • Mw, Mn and the relationship between these values or polydispersity Preferably, m takes values between 50 and 200 for the copolymers, that is, when x / y is different from 0 and, in particular, when the ratio x / y has a value between 1 and 4.
  • the polymeric compound of formula (I) is characterized in that the ratio of monomers x / y comprises values between 30 and 0, preferably the ratio x / y has a value between 1 and 4.
  • the variation of this ratio x / y allows to have polymers with trispyrazolylborate groups more or less distant from each other in the polymer chain.
  • the vinyl polyborbornene of formula (I) is characterized in that R 1 , R 2 and R 3 are monovalent groups, the same or different.
  • R 1 , R 2 and R 3 can be independently selected from the group consisting of hydrogen, hydrocarbyl, halogen and pseudohalogen.
  • hydrogen also comprises any of its isotopes.
  • R 1 , R 2 and / or R 3 can be deuterium.
  • R 1 , R 2 and / or R 3 can be a halogen such as fluorine, chlorine, bromine or iodine.
  • R 1 , R 2 and R 3 are bromine.
  • hydrocarbyl is understood as, for example, an aryl, alkyl, alkenyl, alkynyl or heteroaryl group.
  • the hydrocarbyl that may be present in the polymeric compound of formula (I) may be an aryl, alkyl or heteroaryl group.
  • aryl is understood as an aromatic ring formed by carbon atoms, where the ring may contain one or more hydrocarbon substituents or contain heteroatoms, in particular non-depressable groups such as keto, ether, ester, cyano, nitro , sulfonate, amido or thioether.
  • R 1 , R 2 and / or R 3 are a C5-C14 aryl, such as, for example, 2,4,6-trimethylphenyl.
  • alkyl means an aliphatic chain that can be linear, branched or cyclic, and may or may not contain heteroatoms, in particular, non-depressable groups such as keto, ether, ester, cyano, nitro, sulfonate, amido or thioether.
  • R 1 , R 2 and / or R 3 are a CC 8 alkyl such as, for example, methyl.
  • an alkenyl is an aliphatic chain that contains at least one carbon-carbon double bond and can be linear, branched or cyclic.
  • one or more of the substituents R 1 , R 2 and R 3 are a C 2 -C 8 alkenyl. Plus preferably, one or more of the substituents R 1 , R 2 and R 3 are selected from a vinyl group and a C 3 -C 8 allyl group.
  • an alkynyl is an aliphatic chain that contains at least one carbon-carbon triple bond and can be linear, branched or cyclic.
  • one or more of the substituents R 1 , R 2 and R 3 are a C 2 -C 8 alkynyl.
  • heteroaryl is meant an aromatic ring, preferably C 5 -C 6 , where the ring contains a heteroatom that may be preferably N, S or O.
  • halogen any monovalent group assimilable to halogen, for example, -CN or -N0 2 .
  • the substituents R 1 , R 2 and R 3 can be independently selected from the group consisting of hydrogen, methyl, 2,4,6-trimethylphenyl and bromine.
  • R 4 may be hydrogen or hydrocarbyl.
  • R 4 is a hydrocarbyl group. More preferably, R 4 is an alkyl.
  • a CC 8 aliphatic chain that can be linear, branched or cyclic. Particularly preferred alkyl groups are methyl or ethyl.
  • the vinyl polynorbornene of formula (I) comprises a totally aliphatic scaffolding, so that the polymer functionalization is concentrated in the group -Bpz 3 .
  • n is an integer value between 0 and 18.
  • n may have an integer value between 0 and 4.
  • M is a monovalent metal.
  • M can be selected from the group consisting of alkali metal, transition metal of group 11 (Cu, Ag or Au) and thallium.
  • M can be selected from the group consisting of Li, Cu and Ag.
  • the vinyl polynorbornene comprised in the compound of formula (I) of the present invention can be obtained by vinyl addition polymerization of norbornene (bicyclo [2.2.1] hept-2-eno, NB) or its derivatives, and is characterized in that it maintains in its skeleton the bicyclic units of the NB and, therefore, its main chains are completely aliphatic, as the resonance spectra show 13 C nuclear magnetic solution or solid state (CP-MAS).
  • norbornene bicyclo [2.2.1] hept-2-eno, NB
  • R 1 , R 2 , R 3 , R 4 , M, m, n and the x / y ratio maintain the meaning indicated in this document with respect to the vinyl polynorbornene of formula (I).
  • the hydroboration step a) takes place by reacting vinyl polynorbornenes of formula (II) with a hydroboration agent such as, for example, BHBr 2 .SMe 2 , in an organic solvent such as dichloromethane under reflux.
  • a hydroboration agent such as, for example, BHBr 2 .SMe 2
  • organic solvent such as dichloromethane under reflux.
  • this procedure allows the versatile synthesis of trispyrazolylborates with different substituents (R 1 , R 2 , R 3 ) supported in the polymer, which does not limit the obtaining of a wide family of polymeric trispyrazolylborates.
  • the polymers of formula (II) can be synthesized by copolymerization of norbornene and an alkenylnorbornene (V), where R 4 is hydrogen or hydrocarbyl, and n takes integer values between 0 and 18, by use of a Ni (ll) or Pd (ll) catalyst.
  • the ratio x / y in the polymer (II) can be modified by varying the relative proportions of norbornene and alkenylnorbornene (V) in the initial mixture that is subjected to copolymerization.
  • Hydroboration is carried out on said polymer (II), preferably with BHBr 2 SMe 2 in dichloromethane as solvent, at reflux.
  • a basic compound comprising the metal M, preferably LDA (lithium di-isopropylamide), is added, which leads to the polynorbornene with trispyrazolylborate groups of formula (I).
  • the nature of the metal M containing the polymer can be varied either by modifying the base used in step b) of the process, or by including a later step c), where the reaction of the polymer (I) obtained in step b) takes place, preferably M is Li, with a salt of another monovalent metal ( ⁇ ' ), preferably a salt of Cu or Ag.
  • the process described in this patent application comprises a step c), wherein the polymer of formula (I) where M is equal to Li reacts with a copper salt (1), preferably Cul in acetonitrile, or silver (1), preferably AgBF 4 in tetrahydrofuran, giving rise to polymers (I), where M is Cu or Ag, respectively.
  • a copper salt (1) preferably Cul in acetonitrile
  • silver (1) preferably AgBF 4 in tetrahydrofuran
  • the present invention is illustrated by the following examples that should not be considered limiting thereof.
  • the notation used for structural characterization data is shown in the figure.
  • the dibromoborane dimethyl sulfide adduct (21 mL of a 1.0 M solution in CH 2 CI 2 , 21 mmol) is added dropwise onto this solution and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3,5-dimethylpyrazole (8.083 g, 81.08 mmol) is added. After stirring for 16 hours at a temperature between 20-25 ° C, the mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (63.06 mmol) is added dropwise thereto in a mixture of THF and hexane.
  • the solution of lithium diisopropylamide is previously obtained by mixing Li n Bu (39.4 mL of a 1, 6 M in hexane, 63.04 mmol) and NH Pr 2 (9 mL, 63.03 mmol) in THF (50 mL) at -78 ° C.
  • the reaction mixture containing the polymer is stirred for 16 hours while slowly reaching a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is washed repeatedly with acetonitrile (6 x 50 mL).
  • the resulting solid is filtered under nitrogen, washed with acetonitrile (6 x 30 mL) and dried in vacuo.
  • the polymer is obtained as an orange solid (10.62 g, yield: 93%).
  • Example 3
  • dibromoborano-dimethyl sulfide adduct (1, 3 mL of a 1, 0 M in CH 2 Cl 2, 1, 3 mmol) and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3- (2,4,6-trimethylphenyl) pyrazole (0.976 g, 5.24 mmol) is added. After stirring for 40 hours at reflux, the mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (3.93 mmol) in a mixture of THF and hexane is added dropwise thereto.
  • the solution of lithium diisopropylamide is previously obtained by mixing Li n Bu (2.46 mL of a 1, 6 M in hexane, 3.93 mmol) and NH Pr 2 (0.56 mL, 3.93 mmol) in THF (7 mL) at -78 ° C.
  • the reaction mixture containing the polymer is stirred for 30 min at -78 ° C and 90 min at a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is treated with acetonitrile (20 mL).
  • the resulting solid is filtered under nitrogen, washed with acetonitrile (5 x 10 mL) and dried in vacuo.

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Abstract

The invention relates to novel functionalised polymers of formula (I), in which trispyrazolylborate-type ligands attach to the structure of vinyl polynorbornenes. In this way, the novel polymer compound can form coordination compounds with metals having catalytic activity and, after the reaction, the polymer can be separated from the desired product by filtration and be reused. In addition, the invention further relates to a method for producing the functionalised polymers of formula (I).

Description

DESCRIPCIÓN  DESCRIPTION
POLINORBORNENOS DE ADICIÓN VINÍLICA CON GRUPOS TRISPIRAZOLILBORATO Sector de la técnica VINYL ADDITION POLYNORBORNINS WITH TRISPIRAZOLILBORATO GROUPS Technical sector
La presente invención se encuentra dentro del campo de la funcionalización de polímeros. En particular, constituye un avance en la síntesis de polímeros con ligandos capaces de coordinar metales que den lugar a materiales con propiedades de interés para la industria o, si los metales tienen actividad catalítica, que se puedan usar como soporte de catalizadores. En particular, los polímeros que aquí se describen contienen en su estructura ligandos tridentados de tipo trispirazolilborato. Estos ligandos permiten llevar a cabo reacciones de catálisis con éxito y, su introducción en la estructura del polinorborneno de adición vinílica que aquí se describe da lugar a polímeros que pueden utilizarse para obtener catalizadores recuperables y reciclables. The present invention is within the field of polymerization functionalization. In particular, it constitutes an advance in the synthesis of polymers with ligands capable of coordinating metals that give rise to materials with properties of interest to the industry or, if the metals have catalytic activity, which can be used as catalyst support. In particular, the polymers described herein contain in their structure tridentate trispyrazolylborate type ligands. These ligands make it possible to carry out catalysis reactions successfully and, their introduction into the structure of the vinyl addition polynorbornene described herein results in polymers that can be used to obtain recoverable and recyclable catalysts.
Estado de la técnica State of the art
Los llamados ligandos escorpionato son una clase importante de ligandos polidentados que coordinan metales de forma muy eficaz, generalmente ocupando tres posiciones de coordinación adyacentes. Entre ellos, los ligandos de tipo trispirazolilborato (RBpz3 ~ R = H, generalmente; pz = pirazol o pirazol sustituido) han sido ampliamente usados y los complejos metálicos con este ligando se han usado como modelos de los centros activos de ciertas metaloenzimas [M. Sallmann, C. Limberg, Acc. Chem. Res. 2015, 48, 2734-2743] o han dado lugar a propiedades magnéticas de interés para la industria [P. Hamon, J. -Y. Thépot, M. Le Floch, M. -E. Boulon, O. Cador, S. Golhen, L. Ouahab, L. Fadel, J. -Y. Saillard, J.-R. Hamon, Angew. Chem. Int. Ed. 2008, 47, 8687-8691]. Sin embargo, la aplicación más destacada de los ligandos de tipo trispirazolilborato es la síntesis de complejos de fórmula general RBpz3MLn que son catalizadores de un gran número de reacciones de interés para la industria [a) M. M. Díaz-Requejo, A. Caballero, T. R. Belderraín, M. C. Nicasio, S. Trofimenko, P. J. Pérez, J. Am. Chem. Soc. 2002, 124, 978-983. b) N. A. Foley, J. P. Lee, Z. KE, T. B. Gunnoe, T. R. Cundari, Acc. Chem. Res. 2009, 42, 585-597]. Entre ellas cabe destacar aquellas que suponen la funcionalización de árenos o alcanos [a) M. M. Díaz-Requejo, P. J. Pérez, Chem. Rev. 2008, 708, 3379-3394; b) A. Caballero, E. Despagnet-Ayoub, M. M. Díaz-Requejo, A. Díaz-Rodríguez, M. E. González-Núñez, R. Mello, B. K. Muñoz, W.-S. Ojo, G. Asensio, M. Etienne, P. J. Pérez, Science, 2011 , 332, 835-838; c) A. Caballero, P. J. Pérez, J. Organomet. Chem. 2015, 793, 108-113; d) A. Olmos, B. Noverges, A. Caballero, G. Asensio, P. J. Pérez, solicitud de patente No. WO2015/181415 A1 ; e) B. A. McKeown, J. P. Lee, J. Mei, T. R. Cundari, T. B. Gunnoe, Eur. J. Inorg. Chem. 2016, 2296-231 1]. La conversión directa de un enlace C-H de un areno o un alcano en un enlace C-X, con un grupo funcional X deseado, es muy exigente desde el punto de vista químico. Sin embargo resulta muy conveniente, pues supone el empleo directo de las materias primas disponibles sin necesidad de transformarlas en otros reactivos intermedios y llevar a cabo varios pasos de reacción, como ocurre en muchos de los procedimientos convencionales empleados. The so-called scorpionate ligands are an important class of polydentate ligands that coordinate metals very effectively, generally occupying three adjacent coordination positions. Among them, trispyrazolylborate-type ligands (RBpz 3 ~ R = H, generally; pz = pyrazole or substituted pyrazole) have been widely used and metal complexes with this ligand have been used as models of the active centers of certain metalloenzymes [M . Sallmann, C. Limberg, Acc. Chem. Res. 2015, 48, 2734-2743] or have given rise to magnetic properties of interest to the industry [P. Hamon, J. -Y. Thépot, M. Le Floch, M. -E. Boulon, O. Cador, S. Golhen, L. Ouahab, L. Fadel, J. -Y. Saillard, J.-R. Hamon, Angew. Chem. Int. Ed. 2008, 47, 8687-8691]. However, the most prominent application of trispyrazolylborate type ligands is the synthesis of complexes of general formula RBpz 3 ML n that are catalysts of a large number of reactions of interest to the industry [a) MM Díaz-Requejo, A. Caballero , TR Belderraín, MC Nicasio, S. Trofimenko, PJ Pérez, J. Am. Chem. Soc. 2002, 124, 978-983. b) NA Foley, JP Lee, Z. KE, TB Gunnoe, TR Cundari, Acc. Chem. Res. 2009, 42, 585-597]. Among them, it is worth mentioning those that involve the functionalization of the areas or alkanes [a) MM Díaz-Requejo, PJ Pérez, Chem. Rev. 2008, 708, 3379-3394; b) A. Caballero, E. Despagnet-Ayoub, MM Díaz-Requejo, A. Díaz-Rodríguez, ME González-Núñez, R. Mello, BK Muñoz, W.-S. Ojo, G. Asensio, M. Etienne, PJ Pérez, Science, 2011, 332, 835-838; c) A. Caballero, PJ Pérez, J. Organomet. Chem. 2015, 793, 108-113; d) A. Olmos, B. Noverges, A. Caballero, G. Asensio, PJ Pérez, patent application No. WO2015 / 181415 A1; e) BA McKeown, JP Lee, J. Mei, TR Cundari, TB Gunnoe, Eur. J. Inorg. Chem. 2016, 2296-231 1]. The direct conversion of a CH bond of an arene or an alkane into a CX bond, with a desired functional group X, is very chemically demanding. However, it is very convenient, since it involves the direct use of the available raw materials without the need to transform them into other intermediate reagents and carry out several reaction steps, as in many of the conventional procedures used.
La actividad y selectividad de los catalizadores que contienen ligandos de tipo trispirazolilborato, RBpz3 ", se puede modular simplemente variando la naturaleza del grupo R y, sobre todo, los sustituyentes en el fragmento pirazol que lleven a trispirazolilboratos con diferentes características electrónicas y de tamaño. La posibilidad de disponer de una amplia familia de ligandos que permiten un ajuste fino de las características de los complejos metálicos es una ventaja importante de estos derivados. The activity and selectivity of the catalysts containing trispyrazolylborate type ligands, RBpz 3 " , can be modulated simply by varying the nature of the R group and, above all, the substituents in the pyrazole fragment that lead to trispyrazolylborates with different electronic and size characteristics. The possibility of having a wide family of ligands that allow a fine adjustment of the characteristics of the metal complexes is an important advantage of these derivatives.
En la actualidad, uno de los principales retos de la química sintética es conseguir procesos sostenibles para la construcción de moléculas. Para ello es fundamental, entre otros aspectos, conseguir catalizadores más activos y selectivos, así como evitar la generación de residuos tras las reacciones. Una de las estrategias para conseguir este objetivo es el uso de catalizadores soportados en un sólido, de forma que éstos puedan separarse fácilmente de los productos deseados y, adicionalmente, puedan reutilizarse. Al reciclar el catalizador, este proceso evita desecharlo tras cada reacción y permite, de hecho, aumentar la actividad del mismo pues el número total de ciclos catalíticos que proporciona durante su vida útil puede llegar a ser muy alto. At present, one of the main challenges of synthetic chemistry is to achieve sustainable processes for the construction of molecules. For this, it is essential, among other aspects, to obtain more active and selective catalysts, as well as to avoid the generation of waste after the reactions. One of the strategies to achieve this objective is the use of catalysts supported on a solid, so that they can be easily separated from the desired products and, additionally, can be reused. When recycling the catalyst, this process avoids discarding it after each reaction and allows, in fact, to increase its activity since the total number of catalytic cycles that it provides during its useful life can become very high.
Existen algunos precedentes, que se especifican a continuación, de la síntesis de trispirazolilborato unidos a polímeros. En particular, la literatura recoge varios ejemplos de poliestireno al que está unido un grupo trispirazolilborato mediante un grupo arilo intermedio, es decir, Pol-C6H4-BPz3 ~ [a) Y. Qin, C. Cui, F. Jákle, Macromolecules 2008, 41, 2972-297 '4. b) Y. Qin, P. O. Shipman, F. Jákle, Macromol. Rapid Commun. 2012, 33, 562-567; c) P. J. Desrochers, A. J. Pearce, T. R. Rogers, J. S. Rodman, Eur. J. Inorg. Chem. 2016, 2465-2473]. Asimismo, también se ha publicado un ejemplo de un análogo al trispirazolilborato polimérico donde el boro se encuentra unido a un poliestireno, con ramificaciones de polietilénglicol, a través de uno de los sustituyentes heterocíclicos: uno de los grupos pirazol se ha sustituido por un benzotriazol para conseguir Pol- benzotriazolBHpz2 " [P. J. Desrochers, B. M. Besel, A. L. Corken, J. R. Evanov, A. L. Hamilton, D. L. Nutt, R. M. Tarkka, Inorg. Chem. 2011 , 50, 1931-1941]. There are some precedents, which are specified below, of the synthesis of trispyrazolylborate bound to polymers. In particular, the literature collects several examples of polystyrene to which a trispyrazolylborate group is attached by an intermediate aryl group, that is, Pol-C 6 H 4 -BPz 3 ~ [a) Y. Qin, C. Cui, F. Jákle , Macromolecules 2008, 41, 2972-297 '4. b) Y. Qin, PO Shipman, F. Jákle, Macromol. Rapid Commun 2012, 33, 562-567; c) PJ Desrochers, AJ Pearce, TR Rogers, JS Rodman, Eur. J. Inorg. Chem. 2016, 2465-2473]. Likewise, an example of an analogue to polymeric trispyrazolylborate where boron is bound to a polystyrene, with ramifications of polyethylene glycol, through one of the heterocyclic substituents: one of the pyrazole groups has been replaced by a benzotriazole to achieve PolybenzotriazolBHpz 2 " [PJ Desrochers, BM Besel , AL Corken, JR Evanov, AL Hamilton, DL Nutt, RM Tarkka, Inorg. Chem. 2011, 50, 1931-1941].
En todos los casos, sólo se sintetiza el derivado Pol-Bpz3 ", donde pz es pirazol. Esto supone una importante limitación para la aplicación posterior del polímero funcionalizado, ya que no se modifica la naturaleza de los sustituyentes en el fragmento pirazol y, en consecuencia, no es posible ajustar la actividad y selectividad de los catalizadores que contienen ligandos de tipo trispirazolilborato, RBpz3 ". In all cases, only the Pol-Bpz 3 " derivative, where pz is pyrazole, is synthesized. This is an important limitation for the subsequent application of the functionalized polymer, since the nature of the substituents in the pyrazole fragment is not modified and, consequently, it is not possible to adjust the activity and selectivity of catalysts containing trispyrazolylborate type ligands, RBpz 3 " .
La presente invención proporciona nuevos polímeros funcionalizados de fórmula (I), donde ligandos de tipo trispirazolilborato se anclan a la estructura de polinorbornenos vinílicos. Estos polímeros son capaces de resistir condiciones de reacción tanto suaves como más exigentes. De este modo, el nuevo compuesto polimérico puede coordinar metales con actividad catalítica y, tras la reacción, el polímero se puede separar por filtración del producto deseado y volver a reutilizarse. El polinorborneno de adición vinílica tiene un esqueleto policíclico completamente alifático, que ha demostrado una estabilidad notable como soporte en otros procesos catalíticos en los que se ha empleado. Así, polinorbornenos de adición vinílica estannilados son reactivos reciclables en reacciones de acoplamiento de Stille catalizadas por paladio [a) A. C. Albéniz, J. C. Casares, P. Espinet, B. Martín-Ruiz, M. M. Villavieja, R. Benavente, solicitud de patente No. ES2237309 A1 , 2003. b) N. Carrera, E. Gutiérrez, R. Benavente, M. M. Villavieja, A. C. Albéniz, P. Espinet, Chem. Eur. J. 2008, 14, 10141-10148; c) A. C. Albéniz, S. Martínez-Arranz, P. Espinet, solicitud de patente No. WO2012160228 A1/ ES201 10030827, 2011. d) S. Martínez-Arranz, N. Carrera, A. C. Albéniz, P. Espinet, A. Vidal-Moya, Adv. Synth. Catal., 2012, 354, 3551-3560]. También se han empleado polinorbornenos de adición vinílica como soporte de organocatalizadores tipo carbeno o prolina con excelente reciclabilidad [a) J. A. Molina de la Torre, A. C. Albéniz, ChemCatChem, 2014, 6, 3547-3552; b) I. K. Sagamanova, S. Sayalero, S. Martínez- Arranz, A. C. Albéniz, M. A. Pericás, Catal. Sci. Technol., 2015, 5, 754-764]. Así mismo, se han utilizado polinorbornenos vinílicos funcionalizados con ligandos carbeno para anclar complejos de paladio, así como la utilización de estos polímeros funcionalizados como catalizadores en reacciones de formación de enlaces C-C de Suzuki o Negishi [J. A. Molina de la Torre, A. C. Albéniz, ChemCatChem, 2016, 8, 2241-2248]. The present invention provides new functionalized polymers of formula (I), where trispyrazolylborate type ligands are anchored to the structure of vinyl polynorbornenes. These polymers are capable of withstanding both mild and more demanding reaction conditions. In this way, the new polymeric compound can coordinate metals with catalytic activity and, after the reaction, the polymer can be filtered off the desired product and reused. The vinyl addition polynorbornene has a completely aliphatic polycyclic skeleton, which has demonstrated remarkable stability as a support in other catalytic processes in which it has been used. Thus, stanyl vinyl addition polynorbornenes are recyclable reagents in Stille coupling reactions catalyzed by palladium [a) AC Albéniz, JC Casares, P. Espinet, B. Martín-Ruiz, MM Villavieja, R. Benavente, patent application No. ES2237309 A1, 2003. b) N. Carrera, E. Gutiérrez, R. Benavente, MM Villavieja, AC Albéniz, P. Espinet, Chem. Eur. J. 2008, 14, 10141-10148; c) AC Albéniz, S. Martínez-Arranz, P. Espinet, patent application No. WO2012160228 A1 / ES201 10030827, 2011. d) S. Martínez-Arranz, N. Carrera, AC Albéniz, P. Espinet, A. Vidal -Moya, Adv. Synth Catal., 2012, 354, 3551-3560]. Vinyl addition polynorbornenes have also been used as a support for carbine or proline type organocatalysts with excellent recyclability [a) JA Molina de la Torre, AC Albéniz, ChemCatChem, 2014, 6, 3547-3552; b) IK Sagamanova, S. Sayalero, S. Martínez- Arranz, AC Albéniz, MA Pericás, Catal. Sci. Technol., 2015, 5, 754-764]. Likewise, vinyl polynorbornenes functionalized with carbeno ligands have been used to anchor palladium complexes, as well as the use of these functionalized polymers as catalysts in reactions of formation of CC bonds of Suzuki or Negishi [JA Molina de la Torre, AC Albéniz, ChemCatChem, 2016, 8, 2241-2248].
Todas las aplicaciones anteriores se basan en la funcionalización de polinorbornenos de adición vinílica que contienen grupos alquilbromo o alquilazido. Sin embargo, estos derivados no son precursores adecuados para la introducción de grupos -Bpz3. Por ello, la presente invención parte de polinorbornenos de adición vinílica (II) que contienen grupos alquenilo "colgantes" a lo largo de la cadena polimérica. De este modo, el método aquí descrito permite obtener, a partir estos polímeros de fórmula (II), polímeros con grupos - Bpz3 anclados a un polímero completamente alifático, tanto en su esqueleto como en las cadenas que unen los -Bpz3 a dicho esqueleto. All of the above applications are based on the functionalization of vinyl addition polynorbornenes containing alkyl bromine or alkylazide groups. However, these derivatives are not suitable precursors for the introduction of -Bpz 3 groups. Therefore, the present invention starts with vinyl (II) polynorbornenes containing "pendant" alkenyl groups along the polymer chain. In this way, the method described here allows to obtain, from these polymers of formula (II), polymers with - Bpz 3 groups anchored to a completely aliphatic polymer, both in their skeleton and in the chains that bind - Bpz 3 to said skeleton.
Una importante ventaja del polímero de fórmula (I) que se describe en esta solicitud de patente es que puede obtenerse mediante una síntesis sencilla, y los grupos pirazol presentes en el ligando Pol-Bpz3 ~ pueden ser cualquier pirazol, con o sin sustituyentes. Esta versatilidad supone una gran ventaja para su aplicación posterior. Otra ventaja adicional del polímero de fórmula (I) es que la unión entre el grupo -Bpz3 y el polinorborneno vinílico tiene lugar mediante una cadena alquílica, más flexible que los anclajes arílicos usados anteriormente. An important advantage of the polymer of formula (I) described in this patent application is that it can be obtained by simple synthesis, and the pyrazole groups present in the Pol-Bpz 3 ~ ligand can be any pyrazole, with or without substituents. This versatility is a great advantage for later application. Another additional advantage of the polymer of formula (I) is that the bond between the -Bpz 3 group and the vinyl polynorbornene takes place by an alkyl chain, more flexible than the previously used aryl anchors.
Descripción de la invención Description of the invention
La presente invención proporciona un compuesto perteneciente a una nueva familia de polinorbornenos de adición vinílica con grupos trispirazolilborato. En particular, la presente invención se refiere a un polinorborneno vinílico de fórmula (I) The present invention provides a compound belonging to a new family of vinyl addition polynorbornenes with trispyrazolylborate groups. In particular, the present invention relates to a vinyl polynorbornene of formula (I)
Figure imgf000006_0001
Figure imgf000006_0001
donde where
R1 , R2 y R3 son grupos monovalentes iguales o distintos; R 1 , R 2 and R 3 are the same or different monovalent groups;
R4 es hidrógeno o hidrocarbilo; R 4 is hydrogen or hydrocarbyl;
M es un metal monovalente;  M is a monovalent metal;
m toma valores entre 25 y 200;  m takes values between 25 and 200;
n toma valores enteros entre 0 y 18; y  n takes integer values between 0 and 18; Y
la relación x/y toma valores entre 30 y 0. Para cada polímero concreto, m es un valor variable en función de la distribución de pesos moleculares de los distintos polímeros iniciales (Mw, Mn y la relación entre estos valores o polidispersidad). Preferentemente, m toma valores entre 50 y 200 para los copolímeros, es decir, cuando x/y es diferente de 0 y, en particular, cuando la relación x/y tiene un valor entre 1 y 4. En otras realizaciones preferentes, m toma un valor entre 25 y 50 para el homopolímero (es decir, cuando x/y = 0).  The ratio x / y takes values between 30 and 0. For each specific polymer, m is a variable value depending on the molecular weight distribution of the different initial polymers (Mw, Mn and the relationship between these values or polydispersity). Preferably, m takes values between 50 and 200 for the copolymers, that is, when x / y is different from 0 and, in particular, when the ratio x / y has a value between 1 and 4. In other preferred embodiments, m takes a value between 25 and 50 for the homopolymer (that is, when x / y = 0).
El compuesto polimérico de fórmula (I) se caracteriza porque la relación de monómeros x/y comprende valores entre 30 y 0, preferentemente la relación x/y tiene un valor entre 1 y 4. La variación de esta relación x/y permite disponer de polímeros con grupos trispirazolilborato más o menos distantes entre sí en la cadena polimérica. De este modo, en el polímero de fórmula (I) se puede favorecer la interacción de un sólo grupo -Bpz3 o dos con un metal de transición con diferentes posibilidades de coordinación e incluso diferentes números de oxidación, lo que puede ser importante en función de la aplicación que se quiera dar al polínorborneno vinílico de fórmula (I). The polymeric compound of formula (I) is characterized in that the ratio of monomers x / y comprises values between 30 and 0, preferably the ratio x / y has a value between 1 and 4. The variation of this ratio x / y allows to have polymers with trispyrazolylborate groups more or less distant from each other in the polymer chain. Thus, in the polymer of formula (I) it is possible to favor the interaction of a single group -Bpz 3 or two with a transition metal with different coordination possibilities and even different oxidation numbers, which may be important depending on of the application that is to be given to the vinyl polyborbornene of formula (I).
Estos compuestos de fórmula (I) son muy poco solubles en disolventes orgánicos, tanto menos solubles cuanto mayor es la relación x/y. These compounds of formula (I) are very slightly soluble in organic solvents, the less soluble the higher the x / y ratio.
El polínorborneno vinílico de fórmula (I) se caracteriza porque R1 , R2 y R3 son grupos monovalentes, iguales o distintos. En realizaciones particulares de la presente invención, R1 , R2 y R3 se pueden seleccionar independientemente del grupo que consiste en hidrógeno, hidrocarbilo, halógeno y pseudohalógeno. The vinyl polyborbornene of formula (I) is characterized in that R 1 , R 2 and R 3 are monovalent groups, the same or different. In particular embodiments of the present invention, R 1 , R 2 and R 3 can be independently selected from the group consisting of hydrogen, hydrocarbyl, halogen and pseudohalogen.
En esta solicitud de patente debe entenderse que el término "hidrógeno" también comprende cualquiera de sus isótopos. En particular, R1 , R2 y/o R3 pueden ser deuterio. In this patent application it should be understood that the term "hydrogen" also comprises any of its isotopes. In particular, R 1 , R 2 and / or R 3 can be deuterium.
Adicionalmente, R1 , R2 y/o R3 pueden ser un halógeno tal como flúor, cloro, bromo o yodo. Preferentemente, uno o varios de los sustituyentes R1 , R2 y R3 son bromo. Additionally, R 1 , R 2 and / or R 3 can be a halogen such as fluorine, chlorine, bromine or iodine. Preferably, one or more of the substituents R 1 , R 2 and R 3 are bromine.
De acuerdo con el conocimiento general común en este sector de la técnica, por hidrocarbilo se entiende, por ejemplo, un grupo arilo, alquilo, alquenilo, alquinilo o heteroarilo. Preferentemente, el hidrocarbilo que puede estar presente en el compuesto polimérico de fórmula (I) puede ser un grupo arilo, alquilo o heteroarilo. According to the general common knowledge in this sector of the art, hydrocarbyl is understood as, for example, an aryl, alkyl, alkenyl, alkynyl or heteroaryl group. Preferably, the hydrocarbyl that may be present in the polymeric compound of formula (I) may be an aryl, alkyl or heteroaryl group.
En la presente solicitud de patente se entiende por arilo un anillo aromático formado por átomos de carbono, donde el anillo puede contener uno o más sustituyentes hidrocarbonados o que contengan heteroátomos, en particular grupos no deprotonables tal como ceto, éter, ester, ciano, nitro, sulfonato, amido o tioéter. Preferentemente, R1 , R2 y/o R3 son un arilo C5-C14, tal como, por ejemplo, 2,4,6-trimetilfenilo. In the present patent application, aryl is understood as an aromatic ring formed by carbon atoms, where the ring may contain one or more hydrocarbon substituents or contain heteroatoms, in particular non-depressable groups such as keto, ether, ester, cyano, nitro , sulfonate, amido or thioether. Preferably, R 1 , R 2 and / or R 3 are a C5-C14 aryl, such as, for example, 2,4,6-trimethylphenyl.
Adicionalmente, por alquilo se entiende una cadena alifática que puede ser lineal, ramificada o cíclica, y puede contener o no heteroátomos, en particular, grupos no deprotonables como ceto, éter, ester, ciano, nitro, sulfonato, amido o tioéter. Preferentemente, R1 , R2 y/o R3 son un alquilo C C8 tal como, por ejemplo, metilo. Additionally, alkyl means an aliphatic chain that can be linear, branched or cyclic, and may or may not contain heteroatoms, in particular, non-depressable groups such as keto, ether, ester, cyano, nitro, sulfonate, amido or thioether. Preferably, R 1 , R 2 and / or R 3 are a CC 8 alkyl such as, for example, methyl.
En este documento se entiende que un alquenilo es una cadena alifática que contiene al menos un doble enlace carbono-carbono y puede ser lineal, ramificada o cíclica. Preferentemente, uno o varios de los sustituyentes R1 , R2 y R3 son un alquenilo C2-C8. Más preferentemente, uno o varios de los sustituyentes R1 , R2 y R3 se seleccionan entre un grupo vinilo y un grupo alilo C3-C8. In this document it is understood that an alkenyl is an aliphatic chain that contains at least one carbon-carbon double bond and can be linear, branched or cyclic. Preferably, one or more of the substituents R 1 , R 2 and R 3 are a C 2 -C 8 alkenyl. Plus preferably, one or more of the substituents R 1 , R 2 and R 3 are selected from a vinyl group and a C 3 -C 8 allyl group.
De acuerdo con el conocimiento general común en este sector de la técnica, se entiende que un alquinilo es una cadena alifática que contiene al menos un triple enlace carbono- carbono y puede ser lineal, ramificada o cíclica. Preferentemente, uno o varios de los sustituyentes R1 , R2 y R3 son un alquinilo C2-C8. According to common general knowledge in this sector of the art, it is understood that an alkynyl is an aliphatic chain that contains at least one carbon-carbon triple bond and can be linear, branched or cyclic. Preferably, one or more of the substituents R 1 , R 2 and R 3 are a C 2 -C 8 alkynyl.
Por heteroarilo se entiende un anillo aromático, preferentemente C5-C6, donde el anillo contiene un heteroátomo que puede ser preferentemente N, S u O. By "heteroaryl" is meant an aromatic ring, preferably C 5 -C 6 , where the ring contains a heteroatom that may be preferably N, S or O.
Asimismo, por pseudohalogeno se entiende cualquier grupo monovalente asimilable a halógeno, por ejemplo, -CN o -N02. En realizaciones preferentes de la presente invención, los sustituyentes R1 , R2 y R3 se pueden seleccionar independientemente del grupo que consiste en hidrógeno, metilo, 2,4,6-trimetilfenilo y bromo. Also, by pseudohalogen is meant any monovalent group assimilable to halogen, for example, -CN or -N0 2 . In preferred embodiments of the present invention, the substituents R 1 , R 2 and R 3 can be independently selected from the group consisting of hydrogen, methyl, 2,4,6-trimethylphenyl and bromine.
En el compuesto de fórmula (I) que se describe en este documento, R4 puede ser hidrógeno o hidrocarbilo. Preferentemente, R4 es un grupo hidrocarbilo. Más preferentemente, R4 es un alquilo. En particular, una cadena alifática C C8 que puede ser lineal, ramificada o cíclica. Grupos alquilo particularmente preferidos son metilo o etilo. De esta forma, el polinorborneno vinílico de fórmula (I) comprende un andamiaje totalmente alifático, de forma que la funcionalización del polímero se concentra en el grupo -Bpz3. In the compound of formula (I) described herein, R 4 may be hydrogen or hydrocarbyl. Preferably, R 4 is a hydrocarbyl group. More preferably, R 4 is an alkyl. In particular, a CC 8 aliphatic chain that can be linear, branched or cyclic. Particularly preferred alkyl groups are methyl or ethyl. Thus, the vinyl polynorbornene of formula (I) comprises a totally aliphatic scaffolding, so that the polymer functionalization is concentrated in the group -Bpz 3 .
En el compuesto de fórmula (I) que se describe en este documento, n es un valor entero entre 0 y 18. Preferentemente, n puede tener un valor entero entre 0 y 4. In the compound of formula (I) described herein, n is an integer value between 0 and 18. Preferably, n may have an integer value between 0 and 4.
En el polinorborneno vinílico de fórmula (I) de la presente invención, M es un metal monovalente. En particular, M se puede seleccionar del grupo que consiste en metal alcalino, metal de transición del grupo 11 (Cu, Ag o Au) y talio. Preferentemente, M se puede seleccionar del grupo que consiste en Li, Cu y Ag. In the vinyl polynorbornene of formula (I) of the present invention, M is a monovalent metal. In particular, M can be selected from the group consisting of alkali metal, transition metal of group 11 (Cu, Ag or Au) and thallium. Preferably, M can be selected from the group consisting of Li, Cu and Ag.
El polinorborneno vinílico comprendido en el compuesto de fórmula (I) de la presente invención puede obtenerse mediante polimerización por adición vinílica de norborneno (biciclo[2.2.1]hept-2-eno, NB) o sus derivados, y se caracteriza porque mantiene en su esqueleto las unidades bicíclicas del NB y, por tanto, sus cadenas principales son completamente alifáticas, como demuestran los espectros de resonancia magnética nuclear de 13C en disolución o en estado sólido (CP-MAS). Al esqueleto principal del polímero se encuentran unidos grupos que contienen trispirazolilborato de tipo - (CHR4)nBpz3 ~ donde pz es un fragmento de fórmula CR1-CR2-CR3-N-N), y donde R1 , R2 y R3 son grupos monovalentes iguales o diferentes, preferiblemente hidrógeno, hidrocarbilo, halógeno o pseudohalógeno, R4 es hidrógeno o hidrocarbilo, y n comprende valores enteros entre 0 y 18. La presencia de los grupos -Bpz3 en el polinorborneno vinílico de fórmula (I) se evidencia en los registros de resonancia magnética nuclear de 11 B. The vinyl polynorbornene comprised in the compound of formula (I) of the present invention can be obtained by vinyl addition polymerization of norbornene (bicyclo [2.2.1] hept-2-eno, NB) or its derivatives, and is characterized in that it maintains in its skeleton the bicyclic units of the NB and, therefore, its main chains are completely aliphatic, as the resonance spectra show 13 C nuclear magnetic solution or solid state (CP-MAS). Groups containing trispyrazolylborate of the type - (CHR 4 ) n Bpz 3 ~ where pz is a fragment of formula CR 1 -CR 2 -CR 3 -NN) are attached to the polymer backbone, and where R 1 , R 2 and R 3 are the same or different monovalent groups, preferably hydrogen, hydrocarbyl, halogen or pseudohalogen, R 4 is hydrogen or hydrocarbyl, and n comprises integer values between 0 and 18. The presence of the -Bpz 3 groups in the vinyl polynorbornene of formula (I ) is evidenced in the 11 B nuclear magnetic resonance records.
Adicionalmente, esta solicitud de patente describe un procedimiento de síntesis de los polímeros de fórmula (I) de la presente invención, caracterizado porque el procedimiento comprende: Additionally, this patent application describes a synthesis process of the polymers of formula (I) of the present invention, characterized in that the process comprises:
a) hidroboración de un polinorborneno vinílico de fórmula (II) para obtener un compuesto polimérico de fórmula (III); y  a) hydroboration of a vinyl polynorbornene of formula (II) to obtain a polymeric compound of formula (III); Y
Figure imgf000009_0001
Figure imgf000009_0001
b) reacción del compuesto polimérico de fórmula (III) obtenido en la etapa anterior con un derivado de pirazol (IV), seguido de un compuesto básico que comprenda el metal monovalente M para obtener el polinorborneno vinílico de fórmula (I); b) reaction of the polymeric compound of formula (III) obtained in the previous step with a pyrazole derivative (IV), followed by a basic compound comprising the monovalent metal M to obtain the vinyl polynorbornene of formula (I);
Figure imgf000010_0001
Figure imgf000010_0001
I donde  I where
R1 , R2, R3, R4, M, m, n y la relación x/y mantienen el significado indicado en este documento respecto al polinorborneno vinílico de formula (I). R 1 , R 2 , R 3 , R 4 , M, m, n and the x / y ratio maintain the meaning indicated in this document with respect to the vinyl polynorbornene of formula (I).
El procedimiento que se describe en este documento permite utilizar casi cualquier pirazol (IV). Teniendo en cuenta la gran variedad de pirazoles sustituidos disponibles, este procedimiento de síntesis ofrece una gran versatilidad, ya que permite obtener polinorbornenos vinílicos de formula (I) con una amplia gama de grupos trispirazolilborato. The procedure described in this document allows almost any pyrazole (IV) to be used. Taking into account the wide variety of substituted pyrazoles available, this synthesis procedure offers great versatility, since it allows to obtain vinyl polynorbornenes of formula (I) with a wide range of trispyrazolylborate groups.
En particular, la etapa a) de hidroboración tiene lugar mediante reacción de polinorbornenos vinílicos de fórmula (II) con un agente de hidroboración tal como, por ejemplo, BHBr2.SMe2, en un disolvente orgánico tal como diclorometano a reflujo. A diferencia de los procedimientos conocidos en el estado de la técnica, el procedimiento descrito en la presente solicitud de patente permite el anclaje del grupo trispirazolilborato a un polímero a través de un grupo alquilo -(CHR4)nCH2-CH2-, más flexible que los anclajes arílicos hasta ahora usados. Además, este procedimiento permite la síntesis versátil de trispirazolilboratos con diferentes sustituyentes (R1 , R2, R3) soportados en el polímero, lo que no limita la obtención de una amplia familia de trispirazolilboratos poliméricos. In particular, the hydroboration step a) takes place by reacting vinyl polynorbornenes of formula (II) with a hydroboration agent such as, for example, BHBr 2 .SMe 2 , in an organic solvent such as dichloromethane under reflux. Unlike the procedures known in the state of the art, the process described in the present patent application allows the trispyrazolylborate group to be attached to a polymer through an alkyl group - (CHR 4 ) nCH2-CH 2 -, more flexible than the aryl anchors so far used. In addition, this procedure allows the versatile synthesis of trispyrazolylborates with different substituents (R 1 , R 2 , R 3 ) supported in the polymer, which does not limit the obtaining of a wide family of polymeric trispyrazolylborates.
De acuerdo con un modo de realización preferente, los polímeros de fórmula (II) se pueden sintetizar por copolimerización de norborneno y un alquenilnorborneno (V), donde R4 es hidrógeno o hidrocarbilo, y n toma valores enteros entre 0 y 18, mediante el uso de un catalizador de Ni(ll) o de Pd(ll). According to a preferred embodiment, the polymers of formula (II) can be synthesized by copolymerization of norbornene and an alkenylnorbornene (V), where R 4 is hydrogen or hydrocarbyl, and n takes integer values between 0 and 18, by use of a Ni (ll) or Pd (ll) catalyst.
Figure imgf000011_0001
La relación x/y en el polímero (II) se puede modificar variando las proporciones relativas de norborneno y de alquenilnorborneno (V) en la mezcla inicial que se somete a copolimerización.
Figure imgf000011_0001
The ratio x / y in the polymer (II) can be modified by varying the relative proportions of norbornene and alkenylnorbornene (V) in the initial mixture that is subjected to copolymerization.
Sobre dicho polímero (II) se lleva a cabo la hidroboración, preferentemente con BHBr2 SMe2 en diclorometano como disolvente, a reflujo. A este polímero derivado de la hidroboración (III) se añade pirazol o un derivado de pirazol de fórmula general (IV) CR1'- CR2-CR3-N-N), donde R1 , R2 y R3 tienen el mismo significado que en el compuesto de fórmula (I). Posteriormente, se añade un compuesto básico que comprende el metal M, preferiblemente LDA (di-isopropilamiduro de litio), lo que conduce al polinorborneno con grupos trispirazolilborato de fórmula (I). Hydroboration is carried out on said polymer (II), preferably with BHBr 2 SMe 2 in dichloromethane as solvent, at reflux. To this polymer derived from hydroboration (III) is added pyrazole or a pyrazole derivative of the general formula (IV) CR 1 '- CR 2 -CR 3 -NN), where R 1 , R 2 and R 3 have the same meaning than in the compound of formula (I). Subsequently, a basic compound comprising the metal M, preferably LDA (lithium di-isopropylamide), is added, which leads to the polynorbornene with trispyrazolylborate groups of formula (I).
El procedimiento que se describe en este documento puede llevarse a cabo sin necesidad de aislar los intermedios obtenidos en las diferentes etapas del procedimiento, o aislando únicamente uno de estos intermedios. The procedure described in this document can be carried out without the need to isolate the intermediates obtained at the different stages of the process, or by isolating only one of these intermediates.
La naturaleza del metal M que contiene el polímero se puede variar bien modificando la base usada en la etapa b) del procedimiento, o bien incluyendo una etapa c) posterior, donde tiene lugar la reacción del polímero (I) obtenido en la etapa b), preferentemente M es Li, con una sal de otro metal monovalente (Μ'), preferentemente una sal de Cu o Ag. The nature of the metal M containing the polymer can be varied either by modifying the base used in step b) of the process, or by including a later step c), where the reaction of the polymer (I) obtained in step b) takes place, preferably M is Li, with a salt of another monovalent metal (Μ ' ), preferably a salt of Cu or Ag.
De acuerdo con un modo de realización particularmente preferente, el procedimiento que se describe en esta solicitud de patente comprende una etapa c), donde el polímero de fórmula (I) donde M es igual a Li reacciona con una sal de cobre(l), preferiblemente Cul en acetonitrilo, o plata(l), preferiblemente AgBF4 en tetrahidrofurano, dando lugar a los polímeros (I), donde M es Cu o Ag, respectivamente. La solubilidad de los polinorbornenos de adición vinílica con grupos trispirazolilborato es muy baja en un gran número de disolventes orgánicos convencionales. Esto es una ventaja para obtener catalizadores soportados en ligandos poliméricos, pues permite su fácil separación de las mezclas de reacción por simple filtración y su reciclado. Ejemplos According to a particularly preferred embodiment, the process described in this patent application comprises a step c), wherein the polymer of formula (I) where M is equal to Li reacts with a copper salt (1), preferably Cul in acetonitrile, or silver (1), preferably AgBF 4 in tetrahydrofuran, giving rise to polymers (I), where M is Cu or Ag, respectively. The solubility of vinyl addition polynorbornenes with trispyrazolylborate groups is very low in a large number of conventional organic solvents. This is an advantage to obtain catalysts supported in polymeric ligands, since it allows their easy separation of reaction mixtures by simple filtration and recycling. Examples
La presente invención se ilustra mediante los siguientes ejemplos que no deben considerarse limitativos de la misma. La notación empleada para los datos de caracterización estructural se muestra en la figura. The present invention is illustrated by the following examples that should not be considered limiting thereof. The notation used for structural characterization data is shown in the figure.
Figure imgf000012_0001
Figure imgf000012_0001
Ejemplo 1. Síntesis de VA-PNB-NB-(CH2)2B(3,5-diMepz)3Li (3,5-diMepz = 3,5- dimetilpirazol) con x/y = 1 ,25. Se disuelve el polinorborneno vinílico de fórmula VA-PNB-NBCH=CH2, correspondiente al compuesto de fórmula (II) donde n es cero, x/y = 1 ,25, Mw= 45663 Daltons, Mw/Mn = 2,36, m = 80-190 (5 g, 21 ,02 mmol de -CH=CH2) en CH2CI2 (350 mL) bajo nitrógeno. Sobre esta disolución se añade gota a gota el aducto dibromoborano-dimetil sulfuro (21 mL de una disolución 1 ,0 M en CH2CI2, 21 mmol) y la mezcla se mantiene a reflujo durante 5 horas. Se enfría entonces a una temperatura entre 20-25 °C y se añade 3,5-dimetilpirazol (8,083 g, 81 ,08 mmol). Tras agitar durante 16 horas a una temperatura entre 20-25 °C, la mezcla se enfría a -78 °C y sobre ella se añade gota a gota una disolución recién preparada de diisopropilamiduro de litio (63,06 mmol) en una mezcla de THF y hexano. La disolución de diisopropilamiduro de litio se obtiene previamente mediante la mezcla de LinBu (39,4 mL de una disolución 1 ,6 M en hexano, 63,04 mmol) y NH¡Pr2 (9 mL, 63,03 mmol) en THF (50 mL) at -78 °C. La mezcla de reacción que contiene el polímero se agita durante 16 horas mientras alcanza lentamente la una temperatura entre 20-25 °C. Transcurrido este tiempo se evapora a sequedad y el residuo se lava repetidas veces con acetonitrilo (6 x 50 mL). El sólido resultante se filtra bajo nitrógeno, se lava con acetonitrilo (6 x 30 mL) y se seca a vacío. El polímero se obtiene como un sólido naranja (10,62 g, rendimiento: 93%). 13C CP- MAS RMN (100,61 MHz): 157-145 (a, C1 , C3), 1 17-1 10 (a, C2), 72-25 (a, Ca, Cp, poliNB), 25-15 (a, Me3, Me1). 11 B MAS RMN (128,38 MHz): 0,9 (a). IR (neto, crrf1): 1541 , 1415, 1344, 1165, 1034, 781. Example 1. Synthesis of VA-PNB-NB- (CH 2 ) 2B (3,5-diMepz) 3 Li (3,5-diMepz = 3,5-dimethylpyrazole) with x / y = 1,25. The vinyl polynorbornene of formula VA-PNB-NBCH = CH 2 is dissolved, corresponding to the compound of formula (II) where n is zero, x / y = 1.25, Mw = 45663 Daltons, Mw / Mn = 2.36, m = 80-190 (5 g, 21, 02 mmol of -CH = CH 2 ) in CH 2 CI 2 (350 mL) under nitrogen. The dibromoborane dimethyl sulfide adduct (21 mL of a 1.0 M solution in CH 2 CI 2 , 21 mmol) is added dropwise onto this solution and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3,5-dimethylpyrazole (8.083 g, 81.08 mmol) is added. After stirring for 16 hours at a temperature between 20-25 ° C, the mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (63.06 mmol) is added dropwise thereto in a mixture of THF and hexane. The solution of lithium diisopropylamide is previously obtained by mixing Li n Bu (39.4 mL of a 1, 6 M in hexane, 63.04 mmol) and NH Pr 2 (9 mL, 63.03 mmol) in THF (50 mL) at -78 ° C. The reaction mixture containing the polymer is stirred for 16 hours while slowly reaching a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is washed repeatedly with acetonitrile (6 x 50 mL). The resulting solid is filtered under nitrogen, washed with acetonitrile (6 x 30 mL) and dried in vacuo. The polymer is obtained as an orange solid (10.62 g, yield: 93%). 13 C CP- MAS NMR (100.61 MHz): 157-145 (a, C 1 , C 3 ), 1 17-1 10 (a, C 2 ), 72-25 (a, C a , C p , polyNB), 25-15 (a, Me 3 , Me 1 ). 11 B MAS NMR (128.38 MHz): 0.9 (a). IR (net, crrf 1 ): 1541, 1415, 1344, 1165, 1034, 781.
Ejemplo 2. Síntesis de VA-PNB-NB-(CH2)2B(3,5-diMepz)3Li (3,5-diMepz = 3,5- dimetilpirazol) con x/y = 27,4. Este polímero se prepara del mismo modo descrito en el ejemplo 1 , pero partiendo de un polinorborneno vinílico de fórmula VA-PNB-NBCH=CH2 con una relación x/y = 27,4. Dicho polímero se sintetiza por copolimerización de norborneno y 5-vinil-2-norborneno con una relación inicial entre ellos 10: 1. Ejemplo 3. Síntesis de VA-PNB-NB-(CH2)2B(3,5-diMe,4-Brpz)3Li (3,5-diMe,4-Brpz = 3,5-dimetil,4-bromopirazol) con x/y = 1 ,25. Example 2. Synthesis of VA-PNB-NB- (CH 2 ) 2B (3,5-diMepz) 3 Li (3,5-diMepz = 3,5-dimethylpyrazole) with x / y = 27.4. This polymer is prepared in the same manner described in Example 1, but starting from a vinyl polynorbornene of formula VA-PNB-NBCH = CH 2 with a ratio x / y = 27.4. Said polymer is synthesized by copolymerization of norbornene and 5-vinyl-2-norbornene with an initial ratio between them 10: 1. Example 3. Synthesis of VA-PNB-NB- (CH 2 ) 2 B (3,5-diMe, 4-Brpz) 3 Li (3,5-diMe, 4-Brpz = 3,5-dimethyl, 4-bromopyrazole) with x / y = 1,25.
Se disuelve el mismo polinorborneno vinílico de fórmula VA-PNB-NBCH=CH2 utilizado en el Ejemplo 1 (x/y = 1 ,25, 5 g, 21 ,02 mmol de -CH=CH2) en CH2CI2 (350 mL) bajo nitrógeno. Sobre esta disolución se añade gota a gota el aducto dibromoborano-dimetil sulfuro (21 mL de una disolución 1 ,0 M en CH2CI2, 21 mmol) y la mezcla se mantiene a reflujo durante 5 horas. Se enfría entonces a una temperatura entre 20-25 °C y se añade 3,5-dimetil-4- bromopirazol (18,4 g, 105, 1 mmol). Tras agitar durante 48 horas a reflujo, la mezcla amarillenta se enfría a -78 °C y sobre ella se añade gota a gota una disolución recién preparada de diisopropilamiduro de litio (63,06 mmol) en una mezcla de THF y hexano. La disolución de diisopropilamiduro de litio se obtiene previamente mediante la mezcla de LinBu (39,4 mL de una disolución 1 ,6 M en hexano, 63,04 mmol) y NH¡Pr2 (9 mL, 63,03 mmol) en THF (50 mL) a -78 °C. La mezcla de reacción que contiene el polímero se agita durante 16 horas mientras alcanza lentamente la una temperatura entre 20-25 °C. Transcurrido este tiempo se evapora a sequedad y el residuo se lava repetidas veces con acetonitrilo (6 x 50 mL). El sólido resultante se filtra bajo nitrógeno, se lava con acetonitrilo (6 x 30 mL) y se seca a vacío. El polímero se obtiene como un sólido marrón claro (15,69 g, rendimiento: 96%). 13C CP-MAS RMN (100,61 MHz): 158-145 (a, C1 , C3), 106-98 (a, C2), 70-25 (a, Ca, Cp, poliNB), 25-15 (a, Me3, Me1). 1 1 B MAS NMR (128,38 MHz): 2.1 (a). IR (neto, crrf1): 1526, 1416, 1339, 1 160, 1082, 1036, 836, 760, 508. The same vinyl polynorbornene of formula VA-PNB-NBCH = CH 2 used in Example 1 (x / y = 1.25.5 g, 21.02 mmol of -CH = CH 2 ) is dissolved in CH 2 CI 2 ( 350 mL) under nitrogen. The dibromoborane dimethyl sulfide adduct (21 mL) is added dropwise over this solution of a 1.0 M solution in CH 2 CI 2 , 21 mmol) and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3,5-dimethyl-4-bromopyrazole (18.4 g, 105.1 mmol) is added. After stirring for 48 hours at reflux, the yellowish mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (63.06 mmol) in a mixture of THF and hexane is added dropwise thereto. The solution of lithium diisopropylamide is previously obtained by mixing Li n Bu (39.4 mL of a 1, 6 M in hexane, 63.04 mmol) and NH Pr 2 (9 mL, 63.03 mmol) in THF (50 mL) at -78 ° C. The reaction mixture containing the polymer is stirred for 16 hours while slowly reaching a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is washed repeatedly with acetonitrile (6 x 50 mL). The resulting solid is filtered under nitrogen, washed with acetonitrile (6 x 30 mL) and dried in vacuo. The polymer is obtained as a light brown solid (15.69 g, yield: 96%). 13 C CP-MAS NMR (100.61 MHz): 158-145 (a, C 1 , C 3 ), 106-98 (a, C 2 ), 70-25 (a, C a , C p , polyNB) , 25-15 (a, Me 3 , Me 1 ). 1 1 B MAS NMR (128.38 MHz): 2.1 (a). IR (net, crrf 1 ): 1526, 1416, 1339, 1 160, 1082, 1036, 836, 760, 508.
Ejemplo 4. Síntesis de VA-PNB-NB-(CH2)2B(3-Mespz)3Li (3-Mespz = 3-(2,4,6- trimetilfenil)pirazol) con x/y = 1,15. Se disuelve el polinorborneno vinílico de fórmula VA-PNB-NBCH=CH2 correspondiente al compuesto de fórmula (II) donde n es cero, x/y = 1 , 15, Mw= 40727 Daltons, Mw/Mn = 4, m = 40-180 (0,3 g, 1 ,31 mmol de -CH=CH2) en CH2CI2 (30 mL) bajo nitrógeno. Sobre esta disolución se añade gota a gota el aducto dibromoborano-dimetil sulfuro (1 ,3 mL de una disolución 1 ,0 M en CH2CI2, 1 ,3 mmol) y la mezcla se mantiene a reflujo durante 5 horas. Se enfría entonces a una temperatura entre 20-25 °C y se añade 3-(2,4,6- trimetilfenil)pirazol (0,976 g, 5,24 mmol). Tras agitar durante 40 horas a reflujo, la mezcla se enfría a -78 °C y sobre ella se añade gota a gota una disolución recién preparada de diisopropilamiduro de litio (3,93 mmol) en una mezcla de THF y hexano. La disolución de diisopropilamiduro de litio se obtiene previamente mediante la mezcla de LinBu (2,46 mL de una disolución 1 ,6 M en hexano, 3,93 mmol) y NH¡Pr2 (0,56 mL, 3,93 mmol) en THF (7 mL) a -78 °C. La mezcla de reacción que contiene el polímero se agita durante 30 min a -78 °C y 90 min a una temperatura entre 20-25 °C. Transcurrido este tiempo se evapora a sequedad y el residuo se trata con acetonitrilo (20 mL). El sólido resultante se filtra bajo nitrógeno, se lava con acetonitrilo (5 x 10 mL) y se seca a vacío. El polímero se obtiene como un sólido amarillento (0,7025 g, rendimiento: 67%). 13C CP-MAS RMN (100,61 MHz): 154- 148 (a, C1), 145-136 (a, C3, Corto, Cpara), 136-132 (a, Cipso), 132-124 (a, Cmeta), 1 12-100 (a, C2), 65-25 (a, Ca, Cp, poliNB), 25-17 (a, Ar-Me). 1 1 B MAS RM N (128,38 MHz): 3 (br). I R (neto, crrf1): 1449s, 1 100s, 849s, 770s, 441 m. Ejemplo 5. Síntesis de VA-PNB-NB-(CH2)4B(3,5-diMepz)3Li (3,5-diMepz = 3,5- dimetilpirazol) con x/y = 2,12. Example 4. Synthesis of VA-PNB-NB- (CH 2 ) 2 B (3-Mespz) 3 Li (3-Mespz = 3- (2,4,6-trimethylphenyl) pyrazole) with x / y = 1.15 . The vinyl polynorbornene of formula VA-PNB-NBCH = CH 2 corresponding to the compound of formula (II) where n is zero, x / y = 1, 15, Mw = 40727 Daltons, Mw / Mn = 4, m = 40 is dissolved -180 (0.3 g, 1.31 mmol of -CH = CH 2 ) in CH 2 CI 2 (30 mL) under nitrogen. To this solution is added drop by drop dibromoborano-dimethyl sulfide adduct (1, 3 mL of a 1, 0 M in CH 2 Cl 2, 1, 3 mmol) and the mixture is refluxed for 5 hours. It is then cooled to a temperature between 20-25 ° C and 3- (2,4,6-trimethylphenyl) pyrazole (0.976 g, 5.24 mmol) is added. After stirring for 40 hours at reflux, the mixture is cooled to -78 ° C and a freshly prepared solution of lithium diisopropylamide (3.93 mmol) in a mixture of THF and hexane is added dropwise thereto. The solution of lithium diisopropylamide is previously obtained by mixing Li n Bu (2.46 mL of a 1, 6 M in hexane, 3.93 mmol) and NH Pr 2 (0.56 mL, 3.93 mmol) in THF (7 mL) at -78 ° C. The reaction mixture containing the polymer is stirred for 30 min at -78 ° C and 90 min at a temperature between 20-25 ° C. After this time, it evaporates to dryness and the residue is treated with acetonitrile (20 mL). The resulting solid is filtered under nitrogen, washed with acetonitrile (5 x 10 mL) and dried in vacuo. The polymer is obtained as a yellowish solid (0.7025 g, yield: 67%). 13 C CP-MAS NMR (100.61 MHz): 154-148 (a, C 1 ), 145-136 (a, C 3 , C ort , C para ), 136-132 (a, C ipso ), 132-124 (a, C meta ), 1 12-100 (a, C 2 ), 65-25 (a, C a , C p , polyNB), 25-17 (a, Ar-Me). 1 1 B MORE RM N (128.38 MHz): 3 (br). IR (net, crrf 1 ): 1449s, 1 100s, 849s, 770s, 441 m. Example 5. Synthesis of VA-PNB-NB- (CH 2 ) 4 B (3,5-diMepz) 3 Li (3,5-diMepz = 3,5-dimethylpyrazole) with x / y = 2.12.
Este polímero se prepara por el procedimiento descrito en el Ejemplo 1 pero usando como polímero de partida el derivado VA-PNB-NBCH2CH2CH=CH2, correspondiente al compuesto de fórmula (II) donde n es igual a 2 y R4 es hidrógeno, x/y = 2, 12, (2,87 mmol de -CH=CH2 /g polímero) y Mw= 34261 Daltons, Mw/Mn = 1 ,77, m = 55-98, sintetizado por copolimerización de norborneno y 5-(4-but-1 -enilo)-2-norborneno y usando como catalizador [Ni(C6F5)2(SbPh3)2] con una relación inicial entre ellos 50:50: 1 . Rendimiento: 95%. 13C CP-MAS RMN (100,61 MHz): 160-150 (a, C1 , C3), 1 18-1 10 (a, C2), 70-25 (a, Ca, Cp, CH2-CH2, poliNB), 25-15 (a, Me3, Me1). 1 1 B MAS NMR (128,38 MHz): 3 (a). IR (neto, crrf1): 1539s, 1416s, 1344s, 1 166m, 1034s, 774s, 646m, 452m. This polymer is prepared by the procedure described in Example 1 but using as a starting polymer the derivative VA-PNB-NBCH 2 CH 2 CH = CH2, corresponding to the compound of formula (II) where n is equal to 2 and R 4 is hydrogen, x / y = 2.12, (2.87 mmol of -CH = CH 2 / g polymer) and Mw = 34261 Daltons, Mw / Mn = 1.77, m = 55-98, synthesized by norbornene copolymerization and 5- (4-but-1 -enyl) -2-norbornene and using as catalyst [Ni (C 6 F 5 ) 2 (SbPh 3 ) 2] with an initial ratio between them 50:50: 1. Yield: 95%. 13 C CP-MAS NMR (100.61 MHz): 160-150 (a, C 1 , C 3 ), 1 18-1 10 (a, C 2 ), 70-25 (a, C a , C p , CH2-CH2, polyNB), 25-15 (a, Me 3 , Me 1 ). 1 1 B MAS NMR (128.38 MHz): 3 (a). IR (net, crrf 1 ): 1539s, 1416s, 1344s, 1 166m, 1034s, 774s, 646m, 452m.
Ejemplo 6. Síntesis de VA-PNB-NB-(CH2)2B(3,5-diMepz)3Cu(NCMe) (3,5-diMepz = 3,5- dimetilpirazol). Example 6. Synthesis of VA-PNB-NB- (CH 2 ) 2 B (3,5-diMepz) 3 Cu (NCMe) (3,5-diMepz = 3,5-dimethylpyrazole).
Sobre una suspensión de VA-PNB-NB(CH2)2B(pzMe2)3Li preparado según el Ejemplo 1 (10,2401 g, 18,9 mmol) en acetonitrilo (40 mL) en atmósfera de nitrógeno se añade una disolución de Cul (3,6 g, 18,9 mmol) en acetonitrilo (120 mL). La mezcla se agita durante 3 horas a una temperatura entre 20-25 °C. El sólido se filtra bajo nitrógeno, se lava con acetonitrilo desoxigenado (6 x 50 mL) y se seca a vacío. Se obtienen 1 1 ,7324 g, rendimiento: 97%. ICP-MS Cu: 90,485 mg Cu/g polímero. 13C CP-MAS RMN (100,61 MHz):On a suspension of VA-PNB-NB (CH 2 ) 2B (pcs Me2 ) 3 Li prepared according to Example 1 (10.2401 g, 18.9 mmol) in acetonitrile (40 mL) under nitrogen atmosphere a solution is added of Cul (3.6 g, 18.9 mmol) in acetonitrile (120 mL). The mixture is stirred for 3 hours at a temperature between 20-25 ° C. The solid is filtered under nitrogen, washed with deoxygenated acetonitrile (6 x 50 mL) and dried in vacuo. 1.1324 g are obtained, yield: 97%. ICP-MS Cu: 90,485 mg Cu / g polymer. 13 C CP-MAS NMR (100.61 MHz):
155- 145 (a, C1 , C3), 1 17 (br, NCMe), 1 14-100 (a, C2), 65-19 (a, Ca, Cp, poliNB), 19-9 (a, Me3, Me1), 2 (NCMe). 1 1 B MAS NMR (128,38 MHz): -1 .5 (a). 155- 145 (a, C 1 , C 3 ), 1 17 (br, NCMe), 1 14-100 (a, C 2 ), 65-19 (a, C a , C p , polyNB), 19-9 (a, Me 3 , Me 1 ), 2 (NCMe). 1 1 B MAS NMR (128.38 MHz): -1 .5 (a).

Claims

REIVINDICACIONES
1.- Un polinorborneno vinílico de fórmula (I), 1.- A vinyl polynorbornene of formula (I),
Figure imgf000016_0001
donde
Figure imgf000016_0001
where
R1 , R2 y R3 son grupos monovalentes iguales o distintos; R 1 , R 2 and R 3 are the same or different monovalent groups;
R4 es hidrógeno o hidrocarbilo; R 4 is hydrogen or hydrocarbyl;
M es un metal monovalente;  M is a monovalent metal;
m toma valores entre 25 y 200;  m takes values between 25 and 200;
n toma valores enteros entre 0 y 18; y  n takes integer values between 0 and 18; Y
la relación x/y toma valores entre 30 y 0.  the x / y ratio takes values between 30 and 0.
2. - El polinorborneno vinílico según la reivindicación 1 , donde R4 es hidrocarbilo. 2. - The vinyl polynorbornene according to claim 1, wherein R 4 is hydrocarbyl.
3. - Un polinorborneno vinílico con grupos trispirazolilborato según la reivindicación 2, donde R4 es alquilo. 3. - A vinyl polynorbornene with trispyrazolylborate groups according to claim 2, wherein R 4 is alkyl.
4. - El polinorborneno vinílico según cualquiera de las reivindicaciones 1 a 3, donde R1 , R2 y R3 se seleccionan independientemente del grupo que consiste en hidrógeno, hidrocarbilo, halógeno y pseudohalógeno. 4. - The vinyl polynorbornene according to any of claims 1 to 3, wherein R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, hydrocarbyl, halogen and pseudohalogen.
5.- El polinorborneno vinílico según la reivindicación 4, donde el hidrocarbilo se selecciona del grupo que consiste en alquilo, arilo y heteroarilo. 5. The vinyl polynorbornene according to claim 4, wherein the hydrocarbyl is selected from the group consisting of alkyl, aryl and heteroaryl.
6- El polinorborneno vinílico según cualquiera de las reivindicaciones 1 a 5, donde M se selecciona del grupo que consiste en metal alcalino, metal de transición del grupo 11 y talio. 6- The vinyl polyborbornene according to any of claims 1 to 5, wherein M is selected from the group consisting of alkali metal, transition metal of group 11 and thallium.
7- Procedimiento de obtención de un polinorborneno vinílico (I) tal como se define en una cualquiera de las reivindicaciones 1 a 6, caracterizado porque el procedimiento comprende: a) hidroboración de un polinorborneno vinílico de fórmula (II) para obtener un compuesto polimérico de fórmula (III); y 7- Method for obtaining a vinyl polynorbornene (I) as defined in any one of claims 1 to 6, characterized in that the process comprises: a) hydroboration of a vinyl polynorbornene of formula (II) to obtain a polymeric compound of formula (III); Y
Figure imgf000017_0001
Figure imgf000017_0001
b) reacción del compuesto polimérico de fórmula (III) obtenido en la etapa anterior con un derivado de pirazol (IV) seguido de un compuesto básico que comprenda el metal monovalente M para obtener el polinorborneno vinílico de fórmula (I); b) reaction of the polymeric compound of formula (III) obtained in the previous step with a pyrazole derivative (IV) followed by a basic compound comprising the monovalent metal M to obtain the vinyl polynorbornene of formula (I);
Figure imgf000017_0002
Figure imgf000017_0002
Figure imgf000018_0001
Figure imgf000018_0001
I  I
donde where
R1 , R2 y R3 son grupos monovalentes iguales o distintos; R 1 , R 2 and R 3 are the same or different monovalent groups;
R4 es hidrógeno o hidrocarbilo; R 4 is hydrogen or hydrocarbyl;
M es un metal monovalente;  M is a monovalent metal;
m toma valores entre 25 y 200;  m takes values between 25 and 200;
n toma valores enteros entre 0 y 18; y  n takes integer values between 0 and 18; Y
la relación x/y toma valores entre 30 y 0.  the x / y ratio takes values between 30 and 0.
8. - El procedimiento de obtención de un polinorborneno vinílico de fórmula (I) según la reivindicación 7, donde el intermedio obtenido en la etapa a) no se aisla. 8. - The process for obtaining a vinyl polynorbornene of formula (I) according to claim 7, wherein the intermediate obtained in step a) is not isolated.
9. - El procedimiento de obtención de un polinorborneno vinílico de fórmula (I) según cualquiera de las reivindicaciones 7 u 8, donde el polinorborneno vinílico de fórmula (II) se obtiene por copolimerización de norborneno y un alquenilnorborneno (V) en presencia de un catalizador de INI i (I I) o Pd(ll),
Figure imgf000018_0002
9. - The process for obtaining a vinyl polynorbornene of formula (I) according to any of claims 7 or 8, wherein the vinyl polynorbornene of formula (II) is obtained by copolymerization of norbornene and an alkenylnorbornene (V) in the presence of a INI i (II) or Pd (ll) catalyst,
Figure imgf000018_0002
donde where
R4 es hidrógeno o hidrocarbilo, y R 4 is hydrogen or hydrocarbyl, and
n toma valores enteros entre 0 y 18. n takes integer values between 0 and 18.
10. - El procedimiento de obtención de un polinorborneno vinílico de fórmula (I) según cualquiera de las reivindicaciones 7 a 9, donde el procedimiento comprende la reacción de un polinorborneno vinílico de fórmula (I) donde M es un metal monovalente, con una sal de un segundo metal monovalente M', donde M' es un metal monovalente diferente a M, para obtener un segundo polímero de fórmula (I), donde el metal monovalente es M'. 10. - The process for obtaining a vinyl polynorbornene of formula (I) according to any of claims 7 to 9, wherein the process comprises the reaction of a vinyl polynorbornene of formula (I) wherein M is a monovalent metal, with a salt of a second monovalent metal M ' , where M ' is a monovalent metal other than M, to obtain a second polymer of formula (I), where the monovalent metal is M ' .
1 1. El procedimiento de obtención de un polinorborneno vinílico de fórmula (I) según la reivindicación 10, donde el procedimiento comprende la reacción de un polinorborneno vinílico de fórmula (I) donde M es litio, con una sal de un segundo metal monovalente M', donde M ' se selecciona del grupo que consiste en Cu y Ag. 1. The process for obtaining a vinyl polynorbornene of formula (I) according to claim 10, wherein the process comprises the reaction of a vinyl polynorbornene of formula (I) wherein M is lithium, with a salt of a second monovalent metal M ' , where M ' is selected from the group consisting of Cu and Ag.
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EP2314369A1 (en) * 2009-10-23 2011-04-27 Hamilton Sundstrand Corporation Film-based system and method for carbon dioxide separation

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