阅读说明：本技术 通过开环复分解使环烯烃聚合的方法 (Process for polymerizing cycloolefins by ring-opening metathesis ) 是由 M.鲁恩 F.蔡约 P.奎瓦尔 F.特里波托 于 2018-12-20 设计创作，主要内容包括：本发明涉及一种通过开环复分解使环烯烃聚合的方法。该反应在至少一种特定催化剂的存在下进行,该催化剂选自包含至少一个1-芳基-3-环烷基-咪唑啉-2-亚基配体的钌烃亚基配合物和它们的混合物。本发明还涉及用于实施该方法的试剂盒。(The present invention relates to a process for polymerizing cyclic olefins by ring-opening metathesis. The reaction is carried out in the presence of at least one specific catalyst selected from the group consisting of ruthenium hydrocarbon subunit complexes comprising at least one 1-aryl-3-cycloalkyl-imidazolin-2-subunit ligand and mixtures thereof. The invention also relates to a kit for carrying out the method.)

1. A method for polymerizing a cyclic olefin by ring-opening metathesis comprising contacting at least one optionally functionalized cyclic olefin with at least one metathesis catalyst selected from ruthenium hydrocarbon subunit complexes containing at least one 1-aryl-3-cycloalkyl-imidazolin-2-subunit ligand under conditions effective for polymerizing the at least one cyclic olefin.

2. The process of claim 1, wherein the cyclic olefin is selected from the group consisting of bridged cyclic olefins, unbridged cyclic olefins, oligomers thereof, and mixtures thereof.

3. The process according to claim 2, wherein the cyclic olefin is selected from cyclopentadiene, oligomers thereof and mixtures thereof with at least one other cyclic olefin selected from the group consisting of: norbornene, norbornadiene, norbornene dicarboxylic anhydride, cyclohexene, cycloheptene, cyclooctene, cyclododecene and cyclooctadiene, which are optionally functionalized.

4. The process according to any one of claims 1 to 3, wherein the ruthenium complex is selected from compounds of the formula (1),

wherein:

x represents a hydrogen atom or a halogen atom or an alkyl or aryl group,

b represents a cycloalkyl group, and B represents a cycloalkyl group,

ar represents an aryl group optionally substituted with at least one substituent selected from the group consisting of: halogen atoms, and in particular chlorine or fluorine, trifluoromethyl, nitro, alkyl, heteroalkyl or alkylammonium groups and aryl groups substituted by one or more alkyl groups,

l represents a neutral ligand, and L represents a neutral ligand,

a1 represents a hydrogen atom, and,

a2 represents alkyl or alkenyl, aryl or heteroaryl,

or A1 and A2 together form a carbocyclic ring, which is optionally substituted with at least one group selected from alkyl, heteroalkyl, and aryl,

n has a value of 1 or 2.

5. The process according to claim 4, wherein the ruthenium complex is selected from compounds of the formula (1a) or (1b),

wherein B is cycloalkyl; ar is an aryl group which is unsubstituted or substituted by at least one group selected from the group consisting of a halogen atom and trifluoromethyl, nitro, alkyl, heteroalkyl, alkylammonium and aryl; the X groups are independently selected from hydrogen atoms, halogen atoms, aryl groups and alkyl groups; l is an uncharged ligand; a, b, c, d, e and f are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl and phenyl; n has a value of 1 or 2.

6. The method of claim 5, wherein a, c, d, e and f represent hydrogen atoms and b is a phenyl group.

7. The process according to claim 5 or 6, wherein Ar is selected from the group consisting of 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-tris (trifluoromethyl) phenyl, 2,4, 6-trichlorophenyl and hexafluorophenyl, preferably Ar is 2,4, 6-trimethylphenyl.

8. The process according to any one of claims 5 to 7, wherein B is selected from cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl and cyclopentadecyl, preferably B is cyclopentyl or cyclohexyl, more preferably B is cyclohexyl.

9. The method according to any one of claims 5 to 8, wherein each of the groups X represents a hydrogen atom.

10. The process of any one of claims 5 to 9, wherein L is selected from pyridine, phosphine trisubstituted with a group independently selected from alkyl, cycloalkyl and aryl, phosphite trisubstituted with a group independently selected from alkyl, cycloalkyl and aryl, wherein B, Ar and X are as defined in claim 4.

11. Process according to any one of claims 5 to 10, characterized in that it is carried out in the presence of a complex of formula (1B), alone or mixed with a complex of formula (1a), preferably a complex of formula (1a) having the same groups Ar, B and X, wherein the molar ratio of complex of formula (1a) to complex of formula (1B) is advantageously between 99:1 and 1:99, preferably between 5:95 and 95:5, and better still between 30:70 and 70: 30.

12. The process of claim 11, comprising the step of thermally activating the complex of formula (1b) by heating to a temperature of 40-120 ℃ or by adding an activator to the reaction mixture or by a combination of these activation means.

13. The process according to claim 12, wherein the activator is selected from Lewis acids, in particular copper (I) or aluminium halides or of the formula ZnR₂，SnR₂，SnR₄And SiR₄Wherein the radicals R, independently of one another, represent a halogen atom or an alkyl, cycloalkyl, alkenyl, phenyl or benzyl group; bronsted acids, such as organic or inorganic acids, in particular hydrochloric acid, hydrobromic acid, iodic acid, hydrofluoric acid, sulfuric acid, nitric acid, periodic acid, sulfonic acids, for example methanesulfonic acid, mono-and polycarboxylic acids, and also acidic resins.

14. Process according to any one of claims 1 to 13, characterized in that it is carried out in the presence of one or more additives or auxiliaries, in particular organic and/or inorganic fillers; an enhancer; a plasticizer; pigments and/or dyes; an antioxidant; a surfactant or amphiphilic polymer; a flame retardant; an ultraviolet absorber; a light stabilizer; an impact modifier; an antistatic agent; a release agent; a lubricant; a swelling agent; fungicides and mixtures thereof.

15. The method according to claim 14, wherein the filler is selected from the group consisting of fibers, powders, particles, beads, microspheres and particles of any shape based on glass, metal oxides, metal carbides, metal nitrides, ceramics, fly ash or thermoplastic or thermoset polymers or elastomers.

16. The method of claim 15, wherein the fibers are provided in the form of a mat or fabric, and the method comprises the step of impregnating the fibers with a mixture of the at least one cyclic olefin and the at least one metathesis catalyst prior to polymerization.

17. A kit for carrying out the method according to any one of claims 1 to 16, characterized in that it comprises a composition comprising at least one catalyst in encapsulated form dispersed in said at least one cyclic olefin, or comprises two separate compositions, one of which comprises said at least one catalyst and the other of which comprises said at least one cyclic olefin.

18. Use of a catalyst as defined in any one of claims 1 to 16 for the polymerization of at least one optionally functionalized cyclic olefin by ring opening metathesis.

Background

Polydicyclopentadiene or p-DCPD is a polyolefin that is valued for its light weight, stiffness, and its impact resistance, corrosion resistance and high temperature deformation resistance. It is mainly used for the preparation of large-size parts, such as body parts for tractors, buses or trucks.

p-DCPD is typically obtained by the following method: DCPD ring opening metathesis (or ROMP for "ring opening polymerization metathesis") and then crosslinking to give the following product:

this transformation is usually carried out in a mould by the so-called Reaction Injection Moulding (RIM) technique.

The metathesis reaction is generally carried out in the presence of catalysts based on tungsten, molybdenum or ruthenium. However, since tungsten and molybdenum based catalysts are very sensitive to moisture, ruthenium based catalysts are preferred.

Among ruthenium-based catalysts for the polymerization of cycloolefins, mention will be made in particular of those of formula (I):

among them, for example: x1= X2= Cl; r1= phenyl; r2= H; l1 and L2 represent unsaturated nitrogen-containing Heterocyclic carbenes of formula (II) or NHC (for the English "N-Heterocyclic Carbene") type ligands:

as described in patent US-7,652,145, wherein R_a＝R_bIs ═ isopropyl or cyclohexyl, and R_c＝R_dH. Other catalysts of formula (I), but containing multiple phosphines, or one phosphine and one saturated NHC as ligands L1 and L2, include in particular the following nolani ii catalysts:

and catalysts described in document WO 00/46255. First and second generation Grubbs catalysts of the formula:

and catalyst C827 of the formula:

are included in this definition. Their use in the metathesis of cyclic olefins by ring opening is also described in the documents U.S. Pat. No. 5,342,909 and U.S. Pat. No. 6,476,167(Grubbs I) and U.S. Pat. No. 7,329,758(Grubbs II and C827).

Furthermore, it has been reported (F.B. Hamad et al, Olefin metals Ruthenium catalysts bearings unseemmetric Heterocyclic Carbenes,Coordination Chemistry Reviews(2013) http:// dx. doi.org/10.1016/j. ccr.2013.04.015) catalysts containing asymmetric NHC-type ligands, in particular complexes of the formula:

they are believed to be more effective than Grubbs I catalysts (but less effective than Grubbs II catalysts) in the polymerisation of cyclooctadiene and to have activity similar to the complexes comprising symmetric NHC ligands described above.

Other catalysts comprising asymmetric NHC ligands have been proposed as metathesis catalysts (WO 2014/091157). However, they have not been suggested for use in cyclic olefin polymerization by ring opening metathesis.

Applicants have found that Grubbs II catalyst leads to materials with high compressive strength, which is important for many applications, but it does not allow controlled polymerization of cyclic olefins, thus resulting in heterogeneous polymeric materials with bubbles. Other complexes known to date as catalysts for ring-opening metathesis of cyclic olefins do not have the same disadvantages, but the compressive strength of the materials obtained is insufficient. In addition, some of these complexes require the addition of organic solvents (whose effect on the environment is sought to be reduced) to the reaction mixture. In addition, incomplete dissolution of the catalyst in the reaction mixture also results in a heterogeneous material with particles that are potentially fragile to the material formed.

Thus, there remains a need for a metathesis process for cyclic olefins which produces materials having a better compromise of properties (surface appearance and compressive strength) than the ruthenium complexes known for this purpose.

It would also be useful to propose a catalyst system that allows better control of the polymerization than certain catalysts of the prior art (which cause too fast a polymerization, leading to a considerable increase in the viscosity of the reaction mixture, even before the reaction mixture is introduced into the mould, or before the mould is filled, or before the catalyst is suitably dispersed in the resin). This control is particularly critical in the production of large-sized moldings.

Furthermore, it is also useful to propose a more environmentally friendly metathesis process for cyclic olefins in the sense that no or less organic solvent is required in the reaction mixture.

Disclosure of Invention

The applicant has verified that ruthenium hydrocarbon subunit complexes comprising at least one 1-aryl-3-cycloalkyl-imidazoline-2-subunit ligand lead, by ring-opening metathesis of cyclic olefins, to materials with high crushing strength similar to that obtained under the same conditions using Grubbs II catalysts, i.e. differing by less than 5% from the measured values for these materials, which were carried out according to standard D695-15.

Furthermore, these catalysts are sufficiently soluble in the cyclic olefin that no organic solvent needs to be added to the reaction mixture to prevent the formation of particles or bubbles in the material. The absence of organic solvents or the use of smaller amounts of organic solvents not only reduces the environmental impact of the process but also reduces its cost, and in addition, its cost is reduced by using a catalyst that is less costly to prepare than certain other ruthenium complexes.

Finally, these catalysts allow to control the metathesis reactions, thus obtaining materials with a homogeneous appearance.

Accordingly, the present invention relates to a process for polymerizing cyclic olefins by ring-opening metathesis, the process comprising contacting at least one optionally functionalized cyclic olefin with at least one metathesis catalyst selected from ruthenium hydrocarbon subunit complexes containing at least one 1-aryl-3-cycloalkyl-imidazolin-2-subunit ligand under effective conditions for polymerizing the at least one cyclic olefin.

The invention also relates to a kit for carrying out the above method, characterized in that it comprises one composition containing said at least one catalyst in encapsulated form dispersed in said at least one cyclic olefin, or two separate compositions, one of which comprises said at least one catalyst and the other of which contains said at least one cyclic olefin.

The invention also relates to the use of a catalyst as defined above for polymerizing at least one optionally functionalized cyclic olefin by ring-opening metathesis.

In addition to the above advantages, the catalyst used in the process according to the invention allows a suitable control of the polymerization reaction. In addition, they are not sensitive to moisture and are not susceptible to poisoning by impurities present in commercial cycloolefins, so that lower purity cycloolefins can be used.

Detailed Description

Definition of

"halogen" means fluorine, chlorine, bromine or iodine.

"cycloalkyl" refers to a cyclic aliphatic hydrocarbon group, which may be monocyclic or polycyclic. When the group is polycyclic, i.e. when it comprises more than one ring, the rings may advantageously be condensed two by two or linked together two by a bond. Cycloalkyl is, for example, a monocyclic hydrocarbon group having a number of carbon atoms of greater than 2, preferably from 3 to 24, more preferably from 4 to 12, preferably cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl, or a polycyclic (bicyclic or tricyclic) group having a number of carbon atoms of greater than 3, preferably from 6 to 18, for example adamantyl, norbornyl or isopinocampheyl.

"alkyl" means a straight or branched chain saturated alicyclic hydrocarbon group containing from 1 to 12 carbon atoms, in particular methyl, ethyl, isobutyl, octyl or dodecyl. The alkyl group preferably has 1 to 10 carbon atoms, even more preferably 1 to 4 carbon atoms. Examples of preferred alkyl groups are, inter alia, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

"heteroalkyl" refers to a straight or branched hydrocarbon-containing chain having 2 to 15 carbon atoms interrupted by one or more heteroatoms such as N, S or O. The heteroalkyl group may be chosen in particular from polyalkylene groups, alkoxy groups and alkylamino groups.

"alkenyl" means a straight or branched chain unsaturated alicyclic hydrocarbon group containing 2 to 14 carbon atoms, particularly an ethenyl, isopropenyl or butenyl group.

"aryl" refers to a carbocyclic group having from 6 to 20 mono-or polycyclic ring members containing conjugated double bonds. Examples of aryl groups are phenyl and naphthyl.

"heteroaryl" refers to a monocyclic or polycyclic aromatic group, each ring of which comprises 3 to 6 ring members, and wherein at least one ring member comprises a heteroatom, especially thienyl, pyridyl, pyrrolyl, furyl, indolyl, thienyl, benzofuryl, benzothienyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, isoxazolyl, isothiazolyl, quinolinyl, isoquinolinyl.

"carbocyclic" means an aliphatic or aromatic monocyclic or polycyclic hydrocarbon radical containing from 5 to 20 carbon atoms, which is optionally unsaturated, in particular indenyl.

The process according to the invention is a process known as Ring Opening Metathesis Polymerization (ROMP) which consists in contacting at least one optionally functionalized cyclic olefin with at least one specific metathesis catalyst under conditions effective for the polymerization of the at least one cyclic olefin.

"Cyclo-olefin" refers to an optionally bridged monocyclic or polycyclic compound having at least one carbon-carbon double bond. The cycloalkene is advantageously selected from the group consisting of bridged cycloalkenes, unbridged cycloalkenes, oligomers thereof and mixtures thereof. The bridged cycloalkenes are generally reaction products of cyclopentadiene with dienophiles such as dicyclopentadiene, norbornene, norbornadiene and norbornene dicarboxylic anhydrides. The unbridged cyclic olefin may in particular be selected from the group consisting of cyclohexene, cycloheptene, cyclooctene, cyclododecene and cyclooctadiene. Preference is given to using dicyclopentadiene or its oligomers or mixtures thereof with at least one of the other abovementioned cyclic olefins.

In the following, the expressions "dicyclopentadiene" or "DCPD" both denote dicyclopentadiene and its oligomers, unless otherwise stated, it being understood that monomeric dicyclopentadiene is preferred for use in the present invention. Oligomers of DCPD correspond to the formula:

wherein n is 1 to 20, preferably 1 to 10. They include in particular tricyclopentadiene and tetracyclopentadiene.

Mixtures of cyclic olefins allow the properties of the material to be adjusted. In the case of DCPD mixed with another cycloalkene, the molar ratio of DCPD to the other cycloalkene can be, for example, between 1:1 and 1000:1, for example between 2:1 and 50:1, more particularly between 8:1 and 15: 1.

The cycloalkenes used according to the invention may optionally be functionalized. By "functionalized" is meant that one or more hydrogen atoms of the cyclic olefin (or independently of each other) are replaced by a group selected from: alkyl, especially methyl, ethyl, isobutyl, octyl or dodecyl; straight or branched chainAlkenyl, in particular vinyl, isopropenyl or butenyl; -COOR⁵Group, wherein R⁵Is H or alkyl, especially methoxycarbonyl; -OR⁶or-CH 2OR⁶Group, wherein R⁶Is H or alkyl; aryl, preferably phenyl; -COR⁷Group, wherein R⁷Is H or alkyl, especially acetyl; and a cyano group. Examples of functionalized cycloolefins are DCPD-OH and ethylidene norbornene.

In the following, the term "cycloalkene" is used to denote functionalized and unfunctionalized cycloalkenes, it being understood that unfunctionalized cycloalkenes are preferably used. Furthermore, the term denotes both single cyclic olefins and mixtures of different cyclic olefins. It must therefore be understood as equivalent to "one or more cycloolefins".

As mentioned above, in the process according to the invention the cycloalkene is reacted with at least one ruthenium-based catalyst, more precisely a ruthenium hydrocarbon subunit complex comprising at least one 1-aryl-3-cycloalkyl-imidazolin-2-subunit ligand.

"ruthenium hydrocarbylidene complex" means a penta-or hexa-coordinate ruthenium complex containing alkylidene ligands. The ruthenium complexes according to the invention also comprise 1-aryl-3-cycloalkyl-imidazolin-2-ylidene ligands coordinated to the ruthenium atom, whose aryl and imidazolinyl groups may optionally be substituted. Furthermore, it is preferred that the ruthenium complex does not comprise a bidentate ligand. The additional ligand thereof may for example be selected from:

uncharged ligands, in particular of the phosphorus-containing type, such as trialkylphosphines, tricycloalkylphosphines and triarylphosphines, in particular tricyclohexylphosphine or triphenylphosphine, trialkylphosphites or from the group consisting of 1-aryl-3-cycloalkyl-imidazolinyl, and/or

Anionic ligands, such as halides, in particular chlorides.

Thus, in addition to the alkylene ligand and the 1-aryl-3-cycloalkyl-imidazolin-2-ylidene ligand, the ruthenium complex may also contain two anionic ligands and one or two uncharged ligands.

The ruthenium complexes used according to the invention preferably correspond to the following formula (1):

wherein:

x represents a hydrogen or halogen atom or an alkyl or aryl group,

b represents a cycloalkyl group, and B represents a cycloalkyl group,

ar represents an aryl group optionally substituted with at least one substituent selected from: halogen atoms, especially chlorine or fluorine, trifluoromethyl, nitro, alkyl, especially methyl or isopropyl, heteroalkyl, especially alkoxy, for example methoxy, or alkylammonium and aryl substituted by one or more alkyl groups, for example tolyl,

l represents a neutral ligand, and L represents a neutral ligand,

a1 represents a hydrogen atom, and,

a2 represents alkyl or alkenyl, aryl or heteroaryl,

or A1 and A2 together form a carbocyclic ring, which is optionally substituted with at least one selected from alkyl, heteroalkyl, and aryl,

n has a value of 1 or 2.

In one embodiment of the invention, a2 represents vinyl, methyl, thiophenyl or phenyl. In another embodiment, a1 and a2 together form an optionally substituted indenyl.

Preferably, the neutral ligand L is selected from pyridine, phosphine trisubstituted with groups independently selected from alkyl, cycloalkyl and aryl, phosphite or group trisubstituted with groups independently selected from alkyl, cycloalkyl and aryl (L1):

wherein B, Ar and X are as defined above.

It is understood that when n has a value of 2, the ligands L may be different from each other or the same as each other. In one embodiment of the invention, n has the value 1 and L is a phosphine trisubstituted with alkyl or aryl, a phosphite or a group trisubstituted with alkyl or aryl (L1). In another embodiment, n has a value of 2 and each ligand L is pyridine.

Preferably, the complex of formula (1) corresponds to one of the following formulae (1a) and (1 b):

wherein B is cycloalkyl; ar is an aryl group which is unsubstituted or substituted by at least one group selected from the group consisting of a halogen atom and trifluoromethyl, nitro, alkyl, heteroalkyl and aryl; the X groups are independently selected from hydrogen atoms, halogen atoms, aryl groups and alkyl groups; l is an uncharged ligand; a, b, c, d, e and f are independently selected from the group consisting of hydrogen, alkyl, heteroalkyl and phenyl. n has a value of 1 or 2.

According to the invention, B is preferably selected from cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl and cyclopentadecyl. More preferably, B is cyclohexyl.

Further, preferably, Ar is a phenyl group substituted with at least one group selected from a halogen atom, particularly chlorine or fluorine, and a trifluoromethyl group, a nitro group, an alkyl group, particularly a methyl group or an isopropyl group, and an alkoxy group. More preferably, Ar is selected from the group consisting of 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2,4, 6-tris (trifluoromethyl) phenyl, 2,4, 6-trichlorophenyl and hexafluorophenyl. More preferably, Ar is 2,4, 6-trimethylphenyl, also denoted as "mesitylene".

For their part, the groups X preferably each represent a hydrogen atom.

Further, preferably, a, c, d, e and f represent a hydrogen atom, and b represents a phenyl group.

In one embodiment, L is a phosphorus-containing ligand, particularly of the formula P (R)⁸)₃Wherein P is a phosphorus atom and R⁸Selected from the group R⁹And (OR)⁹) Wherein the radical R⁹Are identical or different and are selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, aryl and aralkyl, which areSubstituted or unsubstituted, each group containing up to 20 carbon atoms, and the substituents of said groups being selected from halides, alkyl groups and aryl groups having up to 20 carbon atoms. The aforementioned alkyl, aryl and cycloalkyl groups are as defined above. Very preferably, L is triaryl or trialkyl or tricycloalkylphosphines. An example of a trialkylphosphine is triisopropylphosphine. The tricycloalkylphosphines can be selected in particular from tricyclohexylphosphine and tricyclopentylphosphine. The triarylphosphine may in particular be chosen from triphenylphosphine, tris (methylphenyl) phosphine, mesitylene tertiary phosphine, tris (dimethylphenyl) phosphine and tris [ (trifluoromethyl) phenyl group]A phosphine. As a variant, the ligand L may be a dialkyl or dicycloalkylphosphine, for example selected from dicyclohexylphosphine, di-tert-butylphosphine, di-tert-butylchlorophosphine and 2-isobutyl-2-phospha-bicyclo [ [3.3.1]]Nonane. Very preferably, L is tricyclohexylphosphino.

It is understood that when n has a value of 2, the ligands L may be different from each other or the same as each other. Preferably, n has a value of 1.

Preferred examples of catalysts which can be used according to the invention are described below.

Wherein: PCy3 represents tricyclohexylphosphino, Ph represents phenyl, and iPr represents isopropyl.

In particular, the ruthenium complexes used according to the invention can be prepared by the process described in patent application WO2014/091157 from 1, 3-disubstituted imidazolium salts and ruthenium complex precursors, such as the complex M1 shown below. The ruthenium complex precursor may also be complex M10 shown below.

In a preferred embodiment of the present invention, the metathesis process is carried out in the presence of a complex of the formula (1B), alone or in admixture with a complex of the formula (1a) preferably having identical Ar, B and X groups. The molar ratio of complex of formula (1a) to complex of formula (1b) is advantageously between 99:1 and 1:99, preferably between 5:95 and 95: 5. More preferably, the molar ratio of the complex of formula (1a) to the complex of formula (1b) is from 30:70 to 70: 30.

In the case of using the catalyst of formula (1b) alone or in combination with the catalyst of formula (1a), the process according to the invention also comprises a step of activating these latent catalysts of formula (1b) of the bis-NHC type. Activation may be carried out by heating to a temperature of 40 to 120 ℃ or by adding an activator to the reaction mixture. Different activators may be used, for example Lewis acids, especially halides of copper (I) or aluminum or of the formula ZnR₂，SnR₂，SnR₄And SiR₄Wherein the radicals R, independently of one another, represent a halogen atom or an alkyl, cycloalkyl, alkenyl, phenyl or benzyl radical as described above; bronsted acids, for example organic or inorganic acids, in particular hydrochloric acid, hydrobromic acid, iodic acid, hydrofluoric acid, sulfuric acid, nitric acid, periodic acid, sulfonic acids, for example methanesulfonic acid, mono-and polycarboxylic acids, and also acidic resins. It is also possible to combine a plurality of these activation means, for example inThe catalyst is heated in an acidic medium.

It was observed that the catalysts of formulae (1a) and (1b) allow the process according to the invention to be carried out in open moulds. The combination of the catalysts of formulae (1a) and (1b) allows to benefit from the stability of one and the reactivity of the other to obtain synergistic mixtures.

Hereinafter, "catalyst" will mean a single ruthenium complex and a mixture of ruthenium complexes as described above.

In the process according to the invention, the total amount of catalyst, expressed in moles, relative to the cycloolefin may be, for example, from 10 to 1000ppm, preferably from 30 to 500 ppm.

The metathesis process according to the invention can be carried out in the absence or presence of a solvent, which can be any organic solvent, such as aliphatic hydrocarbons, in particular n-hexane and liquid paraffins; alicyclic hydrocarbons such as cyclohexane or dimethylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing compounds such as acetonitrile; oxygen-containing compounds, in particular ketones, such as acetone; ethers, such as diethyl ether; esters, such as ethyl acetate; and oxygen-containing heterocycles, such as tetrahydrofuran; halogenated compounds such as dichloromethane; and mixtures thereof. The process is preferably carried out in the absence of a solvent.

The process according to the invention is advantageously carried out at atmospheric pressure. The contacting of the catalyst with the cycloolefin is usually carried out with stirring until a homogeneous mixture is obtained, which is then heated. A wide temperature range can be used for this purpose. Thus, the reaction may be carried out at a temperature of 20 to 120 ℃, preferably 40 to 100 ℃ for a time of about 1 minute to 16 hours. Optionally, the reaction mixture may be first heated at 40-60 ℃ for 1 to 20 minutes, then the temperature is raised to 80-100 ℃ and held at the selected value for 1 minute to 16 hours.

The metathesis reaction may be carried out in a mold heated to the aforementioned temperature, according to the Reaction Injection Molding (RIM) method or the Resin Transfer Molding (RTM) method, optionally under vacuum. In the case where the reaction mixture comprises an acid activator, the acid activator may be introduced into the mold after the catalyst and the cyclic olefin are injected and before the mold is heated. As a variant, it is possible to mix the activator with the cycloolefin and the catalyst and then to introduce this mixture into the mould. In the case of activation using an acidic resin, the mixture of catalyst and cyclic olefin is generally passed through the resin before being poured into a mold. As a variant, the metathesis reaction may be carried out after injecting the mixture of cyclic olefin and catalyst into the fibrous preform.

In one embodiment, the process according to the invention can be carried out in the presence of at least one chain transfer agent, such as hex-1-ene, oct-1-ene, vinyl-4-cyclohexene, methyl oleate, pentaphene, carbon tetrachloride, bromotrichloromethane, dodecane-1-thiol, tert-nonanethiol, 4-methylphenylthiol or the reaction product of 1, 8-dimercapto-3, 6-dioxaoctane or a C4-C10 diol with ethylene oxide or propylene oxide and/or a crosslinking agent, such as an organic peroxide.

As a variant or in addition, the process according to the invention may be carried out in the presence of one or more additives or auxiliaries, in particular organic and/or inorganic fillers; an enhancer; a plasticizer; pigments and/or dyes; an antioxidant; a surfactant or amphiphilic polymer; a flame retardant; an ultraviolet absorber; a light stabilizer; an impact modifier; an antistatic agent; a release agent; a lubricant; a swelling agent; fungicides and mixtures thereof.

Examples of fillers are in particular those intended to adjust the density, mechanical properties and/or glass transition temperature of the polymer obtained at the end of the process according to the invention. They may be fibers, powders, particles, beads, microspheres and particles of any shape based on glass, metal oxides, metal carbides, metal nitrides, ceramics, fly ash or thermoplastic or thermoset polymers or elastomers. These fillers may optionally be coated to improve their compatibility with the cycloolefins. They may represent 1 to 200% by weight, relative to the weight of the cycloolefins.

The above-described fillers can be used in particular for the preparation of syntactic foams. In this case, large elements of any shape are generally used as fillers, for example large spheres or glass microbeads, generally hollow and based on thermosetting resins, thermoplastic resins, ceramics or steel. Fillers useful in the preparation of syntactic foams typically have a density of 0.1 to 0.7.

In a first embodiment, the process according to the invention comprises contacting and mixing a first composition comprising a catalyst with a second composition comprising a cyclic olefin under conditions that allow to obtain directly an object of desired shape, for example in a mould or on a preform.

Although the above additives are preferably present in the second composition, they may be added indifferently to the first or second composition. The chain transfer agent and/or crosslinking agent, optionally used, is advantageously present in the second composition.

In this first embodiment, the first composition may consist of the catalyst, generally in powder form, or it may comprise said catalyst in at least one solvent. The solvent may consist of one or more organic solvents (such as those described above) and/or water. One or more surfactants or amphiphilic polymers may optionally be present in the composition, in particular for promoting the formation of an emulsion and/or dispersing the filler optionally present in the first composition or in contact with the latter during mixing of the two compositions.

In this embodiment, the first and second compositions are advantageously mixed in a volume ratio of 50:50 to 99.8: 0.2.

In a second embodiment, the catalyst and the cycloalkene are present in the same composition and the catalyst is encapsulated. It is then necessary to provide mechanical and/or thermal energy to release the catalyst and to react it with the cyclic olefin under conditions that allow the direct obtainment of an object of the desired shape, for example in a mould or on a preform.

In this second embodiment, the catalyst may be contained in solid capsules, the capsules being dispersed in the at least one cyclic olefin or in a composition comprising the at least one cyclic olefin. The encapsulation process advantageously comprises a first step consisting in adding, with stirring, the composition C1 comprising the catalyst to the composition C2 comprising the thermally expandable material or polymerizable liquid,the compositions C1 and C2 were immiscible with each other. In the case where composition C2 comprises a thermally expandable material, the emulsion obtained in the first step is then added, with stirring, to the liquid polymerizable composition C3, compositions C2 and C3 being immiscible with each other, and the emulsion thus obtained is then introduced, with stirring, into the liquid composition C4 comprising the at least one cyclic olefin, compositions C3 and C4 being immiscible with each other. In the case where the composition C2 is polymerizable, after the first step above, the emulsion is added, with stirring, to a liquid composition C3 'comprising the at least one cyclic olefin, the C2 and C3' being immiscible, and the emulsion thus obtained is then charged into a mixer which makes it possible to polymerize it in 1000 to 100000s^-1At a speed of (3) to effect shearing. This step allows the polydisperse droplet population to be split into monodisperse populations of double droplets. In all cases, whatever composition C2, the process was followed by a polymerization step of the droplets obtained. Thereby obtaining solid capsules comprising the catalyst, which are dispersed in the composition comprising the cyclic olefin. Such capsules can be prepared in particular by the processes described in patent applications WO2016/120308 and WO 2017/046360.

The release of the catalyst contained in the solid capsule is initiated by: in the first case, the polymeric rigid envelope of the capsules was broken by a temperature increase which caused the expansion of the heat-expandable material of composition C2, and in the second case, the composition containing the solid capsules was subjected to mechanical shear.

It should be noted that in one or other of the above embodiments, the filler optionally used in the method according to the invention may be present as a variant in the mould in which the method is carried out. In the case of fillers of the large sphere or fiber type, this variant is preferred, in particular when they are used in the preparation of syntactic foams.

More generally, in the case of fibres, the fibres may be provided in the form of a mat or a cloth, in which case the method comprises the steps consisting in: prior to polymerization, the fibers are impregnated with a mixture of the at least one cyclic olefin and the at least one metathesis catalyst.

The invention also relates to a single-component or multi-component kit for carrying out the method according to the invention. The kit comprises a composition comprising at least one catalyst dispersed in said at least one cyclic olefin, in encapsulated form, or two separate compositions, one comprising said at least one catalyst and the other comprising said at least one cyclic olefin.

As mentioned above, the above mentioned cross-linking agent, chain transfer agent and additive may be present in one and/or the other composition of the kit independently of each other.

The method and kit according to the invention can be used for the preparation of land vehicles (in particular tractors, trucks and buses), bodies of marine or aerospace vehicles, blades of wind turbines, sporting goods (such as golf clubs), marine facilities (in particular buoys and pipes), containers for the chemical industry, water treatment equipment, camping equipment, bullet-proof vests, electromagnetic shielding, without this list being limitative. As a variant, the kit according to the invention can be used for repairing cracks in masonry, in particular made of concrete, stone or brick.

Examples

The present invention will be better understood from the following examples, which are given for illustrative purposes only and are not intended to limit the scope of the present invention, which is defined by the appended claims.

Solvents and reagents:

toluene was distilled over sodium benzophenone and degassed before use. Other commercial products were used without prior purification. Ruthenium complexes were supplied by Umicore, Strem Chemicals Inc., or prepared according to procedures described in the literature.

Used in the literature (Mauduit et al,Angew. Chem. Int. Ed.2013,5214103-,ACS Catal.2016,67970-7976). Containing on diaminocarbenesAsymmetric complexes of glycoside groups are described in the literature (Grubbs et al,Organometallics2010,29403-.

Ultrene 99-6 is sold by Cymetech and consists of 94% DCPD and 6 wt% Tri-CPD.

Ethanox 4702 is sold by SI Group.

And (3) chromatography:

analytical thin layer chromatography is at Merck 60F₂₅₄The plate was made of silica-coated aluminum by using 254nm UV light or 3% KMnO4 solution as developer. Purification by column chromatography was performed with Merck 9385 silica gel (230-.

The catalysts given below were used in the examples given below.

A catalyst of formula (1 a):

a catalyst of formula (1 b):