PL220430B1 - Polydicyclopentadiene production process and the use of ruthenium complex - Google Patents

Abstract

The object of the present invention is a method of preparation of polydicyclopentadiene in ring-opening metathesis polymerization in which dicyclopentadiene is polymerized in the presence of a ruthenium (pre)catalyst of general formula 1. The invention relates also to use of a ruthenium (pre)catalyst of general formula 1.

Description

Description of the invention

The invention relates to a process for the preparation of polydicyclopentadiene and the use of ruthenium complexes acting as (pre) catalysts in the ring opening metathetic polymerization (ROMP) reaction of dicyclopentadiene (DCPD).

Olefin metathesis is an important tool in organic synthesis (Handbook of Metathesis, Vol. I-III, Editor: Grubbs, R. H .; Wiley-VCH, 2003).

Many ruthenium complexes actively catalyzing olefin metathesis are known in the art (see reviews: Vougioukalakis, GC; Grubbs, RH Chem. Rev. 2010, 110, 1746. It has been shown that 3rd generation complexes (such as Gru-III, Ind-III) ) are highly useful (pre) catalysts for ROMP-type reactions.

Dec. III Ind. III

Third generation catalysts initiate metathesis reactions very quickly, while in some metathesis applications, such as e.g. mold polymerization, it is preferable to use a (pre) catalyst that does not initiate the reaction immediately after adding it to the substrate but only after appropriate initiation by chemical agents, temperature or light. Complexes characterized by delayed initiation are often referred to as "dormant catalysts"; see reviews: Monsaert, S .; Vila, A. L .; Drozdzak, R .; Van Der Voort, P .; Verpoort, F., Chem. Soc. Rev., 2009, 38, 3360. Examples of "latent catalysts" are complexes, A-F, as well as the recently obtained P-1 and P-2 (oral presentation of results, ISOM XIX, Renes, 10-15.07.2011).

The polymerization of the ROMP type in the form allows to obtain finished products. Polydicyclopentadiene is characterized by, inter alia, low moisture absorption and resistance to stress and high temperatures. Therefore, more and more often vehicle components or specialized tanks for the chemical industry are produced by polymerization of the ROMP type (in the form of dicyclopentadiene).

The P-1 complex has been shown to catalyze the cyclooctadiene ROMP polymerization reaction in dichloromethane at room temperature. However, this reaction takes place with very low substrate conversion. However, in the presence of a chemical activator, the reaction is much faster and with a higher conversion of the substrate. It should be noted, however, that such reactions were carried out with the use of 1 mole% of the (pre) catalyst. It has also been shown (using hydrogen chloride as an example) that the acids activate P-1 and P-2 catalysts by breaking the covalent bond between the ruthenium and nitrogen atoms. As a result, the acid residue of the acid used for activation (the chloride anion in the example shown) becomes the anionic ligand, and the resulting new (pre) catalyst is represented by the formula 1a.

In the course of own research, it was noticed that ruthenium complexes represented by the formula 1:

having a covalent metal-nitrogen bond and phosphorus ligand in their structure do not initiate (or initiate very slowly) the dicyclopentadiene ROMP (DCPD) reaction (conducted without solvent) at 33 ° C. It was surprisingly found, however, that at temperatures of 35 ° C and above, very small amounts (0.01 mol% and less) of the complexes of formula I, after chemical activation, exhibit high catalytic activity and polymerize DCPD very effectively. Furthermore, it was surprisingly found that the complexes of formula 1 wherein one of the neutral ligands L ^1, L ² is a N-heterocyclic carbene ligand, do not require chemical activation and used in an amount equal to or less than 0.01 mole% to effectively catalyze the polymerization reaction of DCPD , at temperatures of 35 ° C and above.

The type of anionic ligand may play a significant role in the efficiency of the (pre) catalyst in the ring-opening metathetic polymerization reaction. It is suspected that the high efficiency of the catalysts of formula D is largely due to a lower degree of bimolecular degradation of the active complex, which in turn is due to the presence of the phenoxide ligand. Catalysts containing phenoxylate or carboxylate anionic ligands are obtained by reacting classic complexes (with anionic chloride ligands) with appropriate phenoxylate or carboxylate salts. This creates additional synthetic problems and increases the time and cost of obtaining the (pre) catalyst. The cost of the catalyst, on the other hand, is a key element determining its applicability in the synthesis of polydicyclopentadiene on an industrial scale, due to its relatively low price. The ease of synthesis, low price and the possibility of introducing a modified anionic ligand into the structure of the complexes of formula 1 by adding an appropriate acid to its mixture with a monomer (e.g. dicyclopentadiene) can determine its industrial utility.

For example, the use of p-toluenesulfonic acid (TsOH) to activate complex 1 allows the preparation of another complex of formula 1b, containing the tosylate anion as anionic ligand.

PL 220 430 B1

Accordingly, the invention relates to a process for the preparation of polydicyclopentadiene by a ring-opening metathetic polymerization reaction in which dicyclopentadiene is polymerized in the presence of a ruthenium (pre) catalyst of the general formula 1

wherein,

X is an anionic ligand;

L ¹ and L ² are neutral ligands;

₁

R ¹ is hydrogen, -C1-20 alkyl, -C2-20 alkenyl, -C2-20 alkynyl or -C5-10 aryl;

R ^2, R ^3, R ⁴ and R ⁵ are independently hydrogen, halogen, C1-C16 alkyl, C1-C16 alkoxy, C1-C16 perfluoroalkyl, C3-C7 cycloalkyl, C2-C16 alkenyl, C5-C14 aryl group, C5-C14 perfluoroaryl, C3-12 heterocyclic, -OR ⁶ , -NO2, -COOH, -COOR ⁶ , -CONR ⁶ R ⁷ , -SO2NR ⁶ R ⁷ , -SO2R ⁶ , -CHO, -COR ⁶ , in which is a group R ⁶ and R ⁷ are each independently a C1-C6 alkyl group, C1-C6 perfluoroalkyl, C5-C14 aryl, C5-C14 perfluoroaryls; R ² , R ³ , R ⁴ and R ⁵ may optionally be joined together to form a substituted or unsubstituted fused -C4-8 carbocyclic ring, or a substituted or unsubstituted fused aromatic ring;

Y is a hydrogen atom, C1-C16 alkyl, C1-C16 perfluoroalkyl, C3-C7 cycloalkyl, C2-C16 alkenyl, C3-C16 cycloalkenyl, C1-C16 alkoxy, C5-C14 aryl, C5-C14 perfluoroaryl, C3-12 heterocyclic , -COOH, -COOR ⁸ , -CONR ⁸ R ⁹ , -SO2NR ⁸ R ⁹ , -SO2R ⁸ , -CHO, COR ⁸ , in which the groups R ⁸ and R ⁹ are independently the group: C1-C6 alkyl, C1- C6 perfluoroalkyl, C5-C10 aryl, C5-C10 perfluoroaryl.

In a preferred embodiment R ¹ , R ² , R ³ , R ⁴ and R ^5, and Y in Formula 1 are as defined above, and

X is a halogen atom, a group -OR ¹⁰ , -O (C = O) R ¹⁰ , -O (SO2) R ¹⁰ , where R ⁴ is a group

C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl which is optionally substituted with at least one C1-C6 alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen group;

₁

L ¹ has the formula P (R ') 3 wherein R' is a C1-12 alkyl, C1-12 alkoxy, C3-12 cycloalkyl, C 5-12 aryl, C 5-12 aryloxy, C 5-12 heterocyclyl;

₂

L ² is an N-heterocyclic carbon ligand (NHC), where (NHC) are compounds such as compounds represented by formulas 2a-2b:

where:

12

R ^11, R ¹² are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl, optionally substituted with at least one C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy group or a halogen atom;

R ^13, R ^14, R ^15, R ¹⁶ are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-14 aryl, optionally substituted with at least one C1-C12 alkyl, C1- C12 perhaloalkyl, C1-C12 alkoxy or halogen, and the radicals R ^13, R ^14, R ^15, R ¹⁶ may optionally be combined together to form a substituted or unsubstituted fused carbocyclic ring -C4-8, or a substituted or unsubstituted fused ring aromatic.

PL 220 430 B1

Preferably, in formula 1, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and Y are as defined above, and

X is a halogen atom, a group -OR ¹⁰ , -O (C = O) R ¹⁰ , -O (SO2) R ¹⁰ , where R ⁴ is a group

C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl which is optionally substituted with at least one C1-C6 alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen group; 12

L ¹ and L ² are each independently described by formula P (R ') 3 wherein R' is a C1-12 alkyl, C3-12 cycloalkyl, C5-14 aryl, C5-12 heterocycle, C1-12 alkoxy, C5-12 aryloxy.

Preferably, in formula 1

X is chlorine;

₁

R ¹ is hydrogen;

R ^2, R ^3, R ⁴ and R ⁵ are independently hydrogen or C1-3 alkyl;

Y represents a hydrogen atom, a C1-C12 alkyl group, -COOH, -COOR ⁸ , -CONR ⁸ R ⁹ , -SO2NR ⁸ R ⁹ ,

-SO2R ⁸ , -CHO, -COR ⁸ in which groups R ⁸ and R ⁹ are independently a C1-C6 alkyl group,

C5-C10 aryl;

₁

L ¹ is triphenylphosphine or tricyclohexylphosphine;

₂

L ² is the ligand of formula 2a or 2b:

where:

12

R ^11, R ¹² are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl,

C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one C1-C6 alkyl group,

C1-C6 perhalogenoalkyl, C1-C6 alkoxy or halogen;

_λ ο ί λ ί c ą ć>

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one C1-C6 _ λ ο ί group c λ ί alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen, and the radicals R ^13, R ^14, R ^15, R ¹⁶ may optionally be combined together to form a substituted or unsubstituted fused carbocyclic ring -C4-8, or a substituted or unsubstituted fused aromatic ring.

In a preferred method, the reaction is carried out in the absence of a solvent.

Preferably, the (pre) catalyst of general formula I is added to the dicyclopentadiene as a solution in an organic solvent.

Preferably, the organic solvent is dichloromethane or toluene.

In a preferred embodiment, the polymerization reaction is initiated by heating the mixture of dicyclopentadiene and the (pre) catalyst of general formula 1 to 35 ° C or more.

Preferably, the polymerization reaction is carried out in the presence of a chemical activator, more preferably, the chemical activator is a Brensted or Lewis acid or a halogen derivative of an alkane or silane, most preferably the chemical activator is hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid.

In a preferred method, the polymerization reaction is carried out at a temperature of 35 to 120 ° C. Preferably, the polymerization reaction is carried out for 1 minute to 24 hours.

In a preferred embodiment, the polymerization reaction is carried out in the presence of the addition of a cross-promoting agent.

Non-limiting examples of preferred cross-linking agents are tert-butyl peroxide, di-tert-butyl peroxide, and mixtures thereof.

Preferably the starting material comprises at least 94% DCPD.

In a preferred embodiment, the polymerization is carried out with an amount of (pre) catalyst equal to or less than 0.01 mol%.

The invention also relates to the use of a ruthenium complex of general formula 1

PL 220 430 B1

wherein all substituents are as defined above, for the preparation of polydicyclopentadiene by metaethical ring-opening polymerization.

The terms of groups not defined below should have the broadest meaning known in the art.

The term "optionally substituted group" means that one or more of the group's hydrogen atoms have been replaced with the groups indicated, provided that such substitution results in a stable compound.

The term "halogen" denotes an element selected from F, Cl, Br, I.

The term "carbene" denotes a particle containing a neutral carbon atom with a valence number of two and two unpaired valence electrons. The term "carbene" also includes carbene analogs in which a carbon atom is replaced with another chemical element; non-limiting examples of such elements are silicon, germanium, nitrogen, phosphorus, sulfur.

The term "alkyl" refers to a saturated, linear or branched hydrocarbon substituent with the indicated number of carbon atoms. Non-limiting examples of alkyl groups are: methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl.

The term "alkoxy" refers to an alkyl substituent as defined above attached through an oxygen atom.

The term "perfluoroalkyl group" denotes an alkyl group as defined above in which all the hydrogen atoms have been replaced with halogens, and the halogens may be the same or different.

The term "cycloalkyl" refers to a saturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Non-limiting examples of a cycloalkyl substituent are -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl.

The term "alkenyl" refers to a non-cyclic, linear or branched hydrocarbon chain of the indicated number of carbon atoms and containing at least one carbon-carbon double bond. Non-limiting examples of alkenyl groups are vinyl, allyl, 1-butenyl, 2-butenyl.

The term "cycloalkenyl" refers to an aliphatic mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms and containing at least one carbon-carbon double bond. Examples of the cycloalkenyl substituent are -cyclopentenyl, -cyclopentadienyl, -cyclohexenyl, -cyclohexadienyl, -cycloheptenyl, -cycloheptadienyl, -cycloheptatrienyl.

The term "aryl group" refers to an aromatic mono- or polycyclic hydrocarbon substituent of the indicated number of carbon atoms. Non-limiting examples of an aryl group are: phenyl, mesityl, anthracene.

The term "heterocyclic group" refers to an aromatic and non-aromatic cyclic substituent of the indicated number of carbon atoms, in which one or more carbon atoms have been replaced by a heteroatom such as nitrogen, phosphorus, sulfur, oxygen with the proviso that there are no two linked in the ring oxygen or sulfur atoms with each other. Non-aromatic heterocyclic groups can have from 4 to 10 ring atoms, while aromatic heterocyclic groups must have at least 5 ring atoms. Heterocyclic groups also include condensed systems with benzene. Non-limiting examples of non-aromatic heterocyclic groups are: pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, dihydropyranyl, tetrahydrothiopyranyl, piperidinyl, morpholino, thiomorpholino, indoline-pyrroline. Non-limiting examples of aromatic heterocyclic groups are groups; pyridinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, furyl, thienyl. The above groups may be attached via a carbon atom or a nitrogen atom. On

For example, the substituent obtained by attaching a pyrrole may be pyrrol-1-yl (N-attached) or pyrrol-3-yl (C-attached).

The term "neutral ligand" refers to an uncharged substituent capable of coordinating with a ruthenium atom. Non-limiting examples of such ligands are: N-heterocyclic carbene ligands, amines, imines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, alkyl and aryl ethers, sulfides, coordinated hydrocarbons, alkyl and aryl halides. Obo12 jętne ligands L ¹ and L ² may be combined with the ligand benzylidenowym (including the nitrogen atom forming a covalent bond with the ruthenium atom), and also may be combined together to form a ligand dwuklesz12 orange (L ¹ -L ^{2), and} further neutral ligands may combine with the anionic ligand X to form multidentate ligands.

The term "anionic ligand" refers to a substituent capable of coordinating with a metal center, having a charge capable of partially or fully compensating for the charge of the metal center. Non-limiting examples of anionic ligands are: fluoride, chloride, bromide, iodide, cyanide, cyanate anions, carboxylic acid anions, alcohol and phenol anions, thiols and thiophenols anions, delocalized charge hydrocarbon anions (e.g. cyclopentadiene anion), acid anions (e.g. cyclopentadiene anion) sulfur and (organo) phosphorus and their esters (such as e.g.

anions of alkylsulfonic and arylsulfonic acids, anions of alkylphosphoric and arylphosphoric acids). The anionic ligand may have L ¹ , L ^{2 groups} linked, for example, such as an acetylacetone anion or a salicylaldehyde anion. Anionic ligand (X) and neutral ligands (L ^1, L ²⁾ can be mutually connected to form a 11 multidentate ligands, like bidentate ligand (X ¹ -L ^1), trójklesz112 orange ligand (X ¹ -L ¹ -L ² ). Non-limiting examples of such ligands are acetyl acetone anion and salicylaldehyde anion.

P r z k ł a d I

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Catalyst P-2 (0.005 mol%) was then added as a solution in dichloromethane and the vial was left in a bath at the same temperature for two hours. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion 83%.

P r z x l a d II

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Catalyst P-2 (0.01 mol%) was then added as a solution in dichloromethane and the vial was transferred to an oil bath at 60 ° C for 15 minutes. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion> 99%.

P r x l a d III

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Then catalyst P-2 (0.005 mol%) was added as a solution in dichloromethane, and hydrogen chloride (0.005 mol%, 4M solution in 1,4-dioxane) was added. The vial was transferred to an oil bath at 60 ° C and left there for 25 minutes. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion> 99%.

P r x l a d IV

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Catalyst P-2 (0.005 mol%) was then added as a solution in dichloromethane and chlorotrimethylsilane (TMSCl) (0.005 mol%) dissolved in a small amount of dichloromethane was added. The vial was transferred to an oil bath at 60 ° C and left there for 60 minutes. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion> 99%.

PL 220 430 B1

P r z k ł a d V

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Catalyst P-2 (0.005 mol%) was then added as a solution in dichloromethane and p-toluenesulfonic acid (p-TsOH) (0.005 mol%) dissolved in a small amount of methanol was then added. The vial was transferred to an oil bath at 60 ° C and left there for 30 minutes. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion> 99%.

P r x l a d VI

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Catalyst P-1 (0.01 mol%) was then added as a solution in dichloromethane, and chlorotrimethylsilane (TMSCl) (0.01 mol%) dissolved in a small amount of dichloromethane was then added. The vial was transferred to an oil bath at 60 ° C and left there for 120 minutes. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion> 99%.

P r o x l a d VII

Preparation of polydicyclopentadiene: Dicyclopentadiene (1 g, 7.56 mmol) was air-charged into a polymerization vial and melted in an oil bath at 35 ° C. Then catalyst P-1 (0.01 mol%) was added as a solution in dichloromethane, and hydrogen chloride (0.01 mol%, 4M solution in 1,4-dioxane) was added. The vial was transferred to an oil bath at 60 ° C and left there for 120 minutes. Toluene was then added to the vial and brought to reflux to wash away unreacted dicyclopentadiene. The insoluble polymer was washed with toluene and dried under reduced pressure at 100 ° C for 12 h. Dicyclopentadiene conversion 90%.

As shown in Examples 1-7, the complexes of Formula 1 according to the invention effectively promote ring opening metathetic polymerization (ROMP) of dicyclopentadiene. Chemical activation of the complexes of formula I with acids allows the easy introduction of various anionic ligands into the structure of the activated complex. Some complexes of general formula I (such as, for example, P-2) can also be thermally activated. The possibility of double activation and "in situ" introduction of anionic ligands makes it possible to precisely control the initiation of the polymerization process as well as to control the time at which the polymerization is completed. In addition, the high stability of the complexes of formula I allows the polymerization process to be carried out in the presence of oxygen, so that there is no need to remove oxygen from commercially available dicyclopentadiene and it is not necessary to use an inert gas atmosphere during the process itself.

Claims (32)

Patent claims 1. Process for the preparation of polydicyclopentadiene by ring-opening metathetic polymerization, characterized by polymerizing dicyclopentadiene in the presence of a ruthenium (pre) catalyst of the general formula 1 PL 220 430 B1 in which, X is an anionic ligand; L ¹ and L ² are neutral ligands; ₁ R ¹ is hydrogen, -C1-20 alkyl, -C2-20 alkenyl, -C2-20 alkynyl or -C5-10 aryl; R ^2, R ^3, R ⁴ and R ⁵ are independently a hydrogen atom, a halogen atom, a C1-C16 alkyl group, C1-C16 alkoxy, C1-C16 perfluoroalkyl, C3-C7 cycloalkyl, C2-C16 alkenyl, C5-C14 aryl, C5-C14 perfluoroaryl, C3-12 heterocycle, group -OR ⁶ , -NO2, -COOH, -COOR ⁶ , -CONR ⁶ R ⁷ , -SO2NR ⁶ R ⁷ , -SO2R ⁶ , -CHO, -COR ⁶ , in which groups R ⁶ and R ⁷ are independently C1-C6 alkyl, C1-C6 perfluoroalkyl, C5-C14 aryl, C5-C14 perfluoroaryl; R ² , R ³ , R ⁴ and R ⁵ may optionally be joined together to form a substituted or unsubstituted fused -C4-8 carbocyclic ring, or a substituted or unsubstituted fused aromatic ring; Y is a hydrogen atom, C1-C16 alkyl, C1-C16 perfluoroalkyl, C3-C7 cycloalkyl, C2-C16 alkenyl, C3-C16 cycloalkenyl, C1-C16 alkoxy, C5-C14 aryl, C5-C14 perfluoroaryl, C3-12 heterocyclic , -COOH, -COOR ⁸ , -CONR ⁸ R ⁹ , -SO2NR ⁸ R ⁹ , -SO2R ⁸ , -CHO, COR ⁸ , in which the groups R ⁸ and R ⁹ are independently the group: C1-C6 alkyl, C1- C6 perfluoroalkyl, C5-C10 aryl, C5-C10 perfluoroaryl. 2. The method according to p. 1, characterized in that in formula 1, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and Z are as defined in claim 1, 1, a X is halogen atom, -OR ¹⁰ , -O (C = O) R ¹⁰ , -O (SO2) R ¹⁰ , where R ⁴ is C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl group, which is optionally substituted with at least one C1-C6 alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen group; ₁ L ¹ has the formula P (R ') 3 wherein R' is a C1-12 alkyl, C1-12 alkoxy, C3-12 cycloalkyl, C 5-12 aryl, C 5-12 aryloxy, C 5-12 heterocyclyl; ₂ L ² is an N-heterocyclic carbon ligand (NHC), where (NHC) are compounds such as compounds represented by formulas 2a-2b: where: 11 12 R ^11, R ¹² are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl, optionally substituted with at least one C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy group or a halogen atom; _λ ο -) / ί -) tz -) ο R ^13, R ^14, R ^15, R ¹⁶ are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-14 aryl, optionally substituted with at least one C1-C12 alki_ Λ Ο - ) Λ -) C group, C1-C12 perhaloalkyl, C1-C12 alkoxy or halogen, and the radicals R ^13, R ^14, R ^15, R ¹⁶ may optionally be combined together to form a substituted or unsubstituted fused carbocyclic ring -C4- 8, or a substituted or unsubstituted fused aromatic ring. 3. The method according to p. 1, characterized in that in formula 1 R ^1, R ^2, R ^3, R ⁴ and R ⁵ and Y are as defined in claim. 1, a X is halogen atom, -OR ¹⁰ , -O (C = O) R ¹⁰ , -O (SO2) R ¹⁰ , where R ⁴ is C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl group, which is optionally substituted with at least one C1-C6 alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen group; L ¹ and L ² are each independently described by formula P (R ') 3 wherein R' is a C1-12 alkyl, C3-12 cycloalkyl, C5-14 aryl, C5-12 heterocycle, C1-12 alkoxy, C5-12 aryloxy. 4. The method according to p. The method of claim 1, characterized in that in formula 1 X is chlorine; ₁ R ¹ is hydrogen; R ^2, R ^3, R ⁴ and R ⁵ are independently hydrogen or C1-3 alkyl; PL 220 430 B1 Y represents a hydrogen atom, a C1-C12 alkyl group, -COOH, -COOR ⁸ , -CONR ⁸ R ⁹ , -SO2NR ⁸ R ⁹ , -SO2R ⁸ , -CHO, -COR ⁸ in which groups R ⁸ and R ⁹ are independently a C1-C6 alkyl group, C5-C10 aryl; ₁ L ¹ is triphenylphosphine or tricyclohexylphosphine; ₂ L ² is the ligand of formula 2a or 2b: where: 11 12 R ^11, R ¹² are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one C1-C6 alkyl group, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen; _ λ Ο _ -) Λ _ -) C _ d> R ^13, R ^14, R ^15, R ¹⁶ are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one C1-C6 _ λ Ο - ) Λ -) C alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen, and the radicals R ^13, R ^14, R ^15, R ¹⁶ may optionally be combined together to form a substituted or unsubstituted fused carbocyclic ring -C4- 8, or a substituted or unsubstituted fused aromatic ring. 5. The method according to one of the claims A process according to any of the preceding claims, characterized in that the reaction is carried out in the absence of a solvent. 6. The method according to p. A process as claimed in claim 1, characterized in that the (pre) catalyst of general formula 1 is added to the dicyclopentadiene as a solution in an organic solvent. 7. The method according to p. 6. The process of claim 6, wherein the organic solvent is dichloromethane or toluene. 8. The method according to p. The process of claim 5, wherein the reaction is initiated by heating the mixture of dicyclopentadiene and the (pre) catalyst of the general formula I to a temperature of 35 ° C or more. 9. The method according to p. The process of claim 1, wherein the polymerization reaction is carried out in the presence of a chemical activator. 10. The method according to p. The process of claim 9, wherein the chemical activator is a Bransted or Lewis acid or a halogen derivative of an alkane or silane. 11. The method according to p. The process of claim 10, wherein the activator is hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid. 12. The method according to any one of claims 1 to 12 The process according to any one of the preceding claims, characterized in that the polymerization reaction is carried out at a temperature from 35 to 120 ° C. 13. The method according to any one of claims 1 to 13 A process as claimed in any one of the preceding claims, characterized in that the polymerization reaction is carried out in 1 minute to 24 hours. 14. The method as claimed in one of claims 1 to 14, The process of any of claims 1-13, characterized in that the polymerization reaction is carried out in the presence of the addition of a cross-promoting agent. 15. The method as claimed in claim 1, The process of any of claims 1-14, characterized in that the starting material comprises at least 94% DCPD. 16. The method according to any one of claims 1 to 16 The process according to 1-15, characterized in that the polymerization is carried out with an amount of (pre) catalyst equal to or less than 0.01 mol%. 17. Use of a ruthenium complex of general formula 1 PL 220 430 B1 in which, X is an anionic ligand; L ¹ and L ² are neutral ligands; ₁ R ¹ is hydrogen, -C1-20 alkyl, -C2-20 alkenyl, -C2-20 alkynyl or -C5-10 aryl; R ^2, R ^3, R ⁴ and R ⁵ are independently hydrogen, halogen, C1-C16 alkyl, C1-C16 alkoxy, C1-C16 perfluoroalkyl, C3-C7 cycloalkyl, C2-C16 alkenyl, C5-C14 aryl group, C5-C14 perfluoroaryl, C3-12 heterocyclic, -OR ⁶ , -NO2, -COOH, -COOR ⁶ , -CONR ⁶ R ⁷ , -SO2NR ⁶ R ⁷ , -SO2R ⁶ , -CHO, -COR ⁶ , in which is a group R ⁶ and R ⁷ are each independently a C1-C6 alkyl group, C1-C6 perfluoroalkyl, C5-C14 aryl, C5-C14 perfluoroaryls; R ² , R ³ , R ⁴ and R ⁵ may optionally be joined together to form a substituted or unsubstituted fused -C4-8 carbocyclic ring, or a substituted or unsubstituted fused aromatic ring; Y is a hydrogen atom, C1-C16 alkyl, C1-C16 perfluoroalkyl, C3-C7 cycloalkyl, C2-C16 alkenyl, C3-C16 cycloalkenyl, C1-C16 alkoxy, C5-C14 aryl, C5-C14 perfluoroaryl, C3-12 heterocyclic , -COOH, -COOR ⁸ , -CONR ⁸ R ⁹ , -SO2NR ⁸ R ⁹ , -SO2R ⁸ , -CHO, COR ⁸ , in which the groups R ⁸ and R ⁹ are independently the group: C1-C6 alkyl, C1- C6 perfluoroalkyl, C5-C10 aryl, C5-C10 perfluoroaryl; for the preparation of polydicyclopentadiene by a metaetic ring-opening polymerization reaction. 123 18. Use according to claim 1 17, characterized in that in formula 1 the substituents R ¹ , R ² , R ³ , R ⁴ and R ⁵ and Y are as defined in claim 1. 17 and X is a halogen atom, a group -OR ¹⁰ , -O (C = O) R ¹⁰ , C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl which is optionally substituted with at least one C1-C6 alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen group; O (SO ₂ ) R ¹⁰ , where R ⁴ is a group L ¹ has the formula P (R ') 3 wherein R' is a C1-12 alkyl, C1-12 alkoxy, C 3-12 cycloalkyl, C5-12 aryl, C5-12 aryloxy, C5-12 heterocyclic; ₂ L ² is an N-heterocyclic carbon ligand (NHC), where (NHC) are compounds such as compounds represented by formulas 2a-2b: where: 11 12 R ^11, R ¹² are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl, optionally substituted with at least one C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy or halogen group; _λ ο _-) / i _-) tz _-) ο R ^13, R ^14, R ^15, R ¹⁶ are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-14 aryl, optionally substituted with at least one C1-C12 alki_ Λ ο - ) Λ -) C group, C1-C12 perhaloalkyl, C1-C12 alkoxy or halogen, and the radicals R ^13, R ^14, R ^15, R ¹⁶ may optionally combine with each other to form a substituted or unsubstituted fused carbocyclic ring, -C4-8, or a substituted or unsubstituted fused aromatic ring. 123 19. The use according to claim 1 17, characterized in that in formula 1 R ¹ , R ² , R ³ , 45 R ⁴ and R ⁵ and Y are as defined in claim 1. 17 and X is a halogen atom, a group -OR ¹⁰ , -O (C = O) R ¹⁰ , -O (SO2) R ¹⁰ , where R ⁴ is a group C1-C12 alkyl, C3-C12 cycloalkyl, C5-C14 aryl which is optionally substituted with at least one C1-C6 alkyl, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen group; 12 L ¹ and L ² are each independently described by formula P (R ') 3 wherein R' is a C1-12 alkyl, C3-12 cycloalkyl, C5-14 aryl, C5-12 heterocycle, C1-12 alkoxy, C5-12 aryloxy. 20. Use according to Claim 17, characterized in that in formula 1 X is chlorine; ₁ R ¹ is hydrogen; R ^2, R ^3, R ⁴ and R ⁵ are independently hydrogen or C1-3 alkyl; PL 220 430 B1 Y represents a hydrogen atom, a C1-C12 alkyl group, -COOH, -COOR ⁸ , -CONR ⁸ R ⁹ , -SO2NR ⁸ R ⁹ , -SO2R ⁸ , -CHO, -COR ⁸ in which groups R ⁸ and R ⁹ are independently a C1-C6 alkyl group, C5-C10 aryl; ₁ L ¹ is triphenylphosphine or tricyclohexylphosphine; ₂ L ² is the ligand of formula 2a or 2b: where: 11 12 R ^11, R ¹² are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one C1-C6 alkyl group, C1-C6 perhaloalkyl, C1-C6 alkoxy or halogen; R ^13, R ^14, R ^15, R ¹⁶ are independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C14 aryl, optionally substituted with at least one C1-C6 alkyl group, C1- C6 perhaloalkyl, C1-C6 alkoxy or halogen, and the radicals R ^13, R ^14, R ^15, R ¹⁶ may optionally be combined together to form a substituted or unsubstituted fused carbocyclic ring -C4-8, or a substituted or unsubstituted fused ring aromatic. 21. Use according to any one of claims 1 to 21 17-20, characterized in that the reaction is carried out in the absence of a solvent. 22. Use according to claim 22 17. A process as claimed in claim 17, characterized in that the (pre) catalyst of general formula 1 is added to the dicyclopentadiene as a solution in an organic solvent. 23. Use according to claim 1 22, characterized in that the organic solvent is dichloromethane or toluene. 24. Use according to claim 24 The process of claim 21, wherein the reaction is initiated by heating the mixture of dicyclopentadiene and the (pre) catalyst of the general formula I to a temperature of 35 ° C or higher. 25. Use according to claim 1 The method of claim 1, wherein the polymerization reaction is carried out in the presence of a chemical activator. 26. Use according to claim 1 The process of claim 25, wherein the chemical activator is a Bransted or Lewis acid or a halogen derivative of an alkane or silane. 27. The use of claim 27 The process of claim 26, wherein the activator is hydrogen chloride, chlorotrimethylsilane or p-toluenesulfonic acid. 28. Use according to any one of claims 1 to 28 17-27, characterized in that the polymerization reaction is carried out at a temperature from 35 to 120 ° C. 29. Use according to any one of claims 1 to 29. 17-28, characterized in that the polymerization reaction takes from 1 minute to 24 hours. 30. Use according to any one of claims 1 to 30. 17-29, characterized in that the polymerization reaction is carried out in the presence of the addition of a cross-promoting agent. 31. Use according to any one of claims 1 to 31 17-30, characterized in that the starting material comprises at least 94% DCPD. 32. Use according to any one of claims 1 to 32. 17-30, characterized in that the polymerization is carried out with an amount of (pre) catalyst equal to or less than 0.01 mol%.