CN114276491A - Liquid ruthenium carbene catalyst composition and its application in preparing cycloolefin resin - Google Patents

Abstract

The present invention provides a liquid ruthenium carbene catalyst composition and its application in preparing cycloolefin resin. Specifically, the present invention provides a liquid catalyst composition containing a ruthenium carbene catalyst, the liquid catalyst composition containing a ruthenium carbene catalyst, a solvent and an optional stabilizer, wherein the solvent contains a C=C structure and an intramolecular carbon Unsaturated acid anhydrides with a number of not more than 20 and/or esters with a C=C structure and a carbon number of not more than 20 in the molecule. The catalytic system can be stored at room temperature and has good storage stability. The liquid catalyst composition is used in combination with the liquid cycloolefin/cycloolefin composition to realize continuous automatic production of thermosetting cycloolefin resin.

Description

Liquid Ruthenium Carbene Catalyst Composition and Its Application in Preparation of Cyclic Olefin Resin

technical field

The present invention relates to a liquid ruthenium carbene catalyst composition and its application in preparing cyclic olefin resin.

Background technique

The ruthenium carbene catalyst is used for the composition containing dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and other cyclic olefins by injection reaction injection molding (RIM), resin die casting molding (RTM) and other process methods. Ring-opening metathesis polymerization (ROMP) has good results, and this type of catalyst has good water and oxygen resistance, and requires less production equipment. However, because the commonly used ruthenium carbene catalyst or the combination of the ruthenium carbene catalyst and the chlorinated paraffin is a solid or highly viscous substance, it is difficult to use it directly in the process of continuous production. Therefore, in the prior art solutions, the ruthenium carbene catalyst is often dissolved in a certain amount of solvent for use. Due to the poor solubility of such catalysts in cyclic olefins represented by DCPD and their compositions and their strong reactivity after mixing with such substances, aromatic hydrocarbons (benzene, toluene, xylene, Toluene, etc.), alkane, cycloalkane, dichloromethane, tetrahydrofuran and ethyl acetate and other weakly polar solutions are used as solvents. However, the ruthenium carbene catalyst in the above-mentioned common solvents may cause the ligands on the catalyst to fall off, resulting in a very short storage time. Usually, the catalyst solution will be deactivated within 24 hours after configuration, and it needs to be prepared and used. In addition, the use of the above-mentioned solvents may also lead to the "surface flow marks" of the cured products of the cycloolefin composition may be aggravated, and the mechanical properties may be deteriorated.

CN112547126A discloses the application of a ruthenium carbene composition, in which a formulation of dicyclopentadiene/epoxy resin composite material is disclosed: dicyclopentadiene and epoxy resin are mixed to form component A, a ruthenium carbene catalyst composition, Methyl-5-norbornene-2,3-dicarboxylic acid anhydride (epoxy curing agent, comonomer), coupling agent KH560 and anti-aging agent to form component B; another kind of dicyclopentane is also disclosed. Formulation of ene/epoxy resin composite material: Dicyclopentadiene and epoxy resin are mixed to form component A, ruthenium carbene catalyst-chlorinated paraffin composition, methyltetrahydrophthalic anhydride (epoxy resin curing agent) , 2-methylimidazole (curing agent accelerator), glass fiber and silane coupling agent A172 are mixed into component B.

CN112662129A discloses a resin composition, a composite material and a preparation method thereof, wherein a formula for preparing polydicyclopentadiene is disclosed: dicyclopentadiene, graphite powder and triphenylphosphine are mixed as component A, The catalyst-chlorinated paraffin composition and methyl-5-norbornene-2,3-dicarboxylic acid anhydride (comonomer) were mixed as the B component. In the methods disclosed in the above two applications, when a ruthenium carbene catalyst and a chlorinated paraffin are preconfigured into a catalyst composition, a high-viscosity material will be formed, which is unfavorable for operation.

Therefore, in order to realize the application of the ruthenium carbene catalyst in the continuous automatic production of polycyclic olefin resin materials, it is necessary to obtain a low-viscosity catalyst solution/dispersion system with storage stability.

SUMMARY OF THE INVENTION

In view of the above-mentioned shortcomings of the prior art, the present invention dissolves the ruthenium carbene catalyst in an unsaturated acid anhydride containing a C=C structure and having no more than 20 carbon atoms in the molecule and/or containing a C=C structure and having no more than 20 carbon atoms in the molecule. In the ester, a stable low-viscosity (≤450mPa·s, 25°C) liquid catalyst composition is formed. The liquid catalyst composition is used in combination with the liquid cycloolefin/cycloolefin composition to realize continuous automatic production of thermosetting cycloolefin resin, and the catalyst system can be stored at room temperature, has good storage stability, and can overcome the above-mentioned problems. There are technical flaws.

Therefore, a first aspect of the present invention provides a liquid catalyst composition containing a ruthenium carbene catalyst, the liquid catalyst composition containing a ruthenium carbene catalyst, a solvent and an optional stabilizer, wherein the solvent contains a C=C-containing structure and Unsaturated acid anhydrides with no more than 20 carbon atoms in the molecule and/or esters with a C=C structure and no more than 20 carbon atoms in the molecule.

In one or more embodiments, the ruthenium carbene catalyst is a Grubbs first-generation catalyst, a Grubbs second-generation catalyst and/or a ruthenium carbene compound as shown in formula I or a salt thereof:

Wherein, R ¹ and R ² in formula I are independently C4-C18 alkyl or C4-C18 alkyl substituted by R ^1-1 ; R ^1-1 is C6-C10 aryl; Mes is mesitylene base; Cy is cyclohexyl.

In one or more embodiments, the C4-C18 alkyl group in the C4-C18 alkyl group or the C4-C18 alkyl group substituted by R ^1-1 may independently be a C4-C10 alkyl group.

In one or more embodiments, in the C4-C18 alkyl substituted by R ^1-1 , the number of R ^1-1 is 1, 2 or 3, and when it is 2 or 3, R ^1-1 same or different.

In one or more embodiments, the C6-C10 aryl group is phenyl or naphthyl.

In one or more embodiments, the R ¹ and R ² are the same or different.

In one or more embodiments, the C4-C18 alkyl in the C4-C18 alkyl or C4-C18 alkyl substituted by R ^1-1 is independently a C4-C6 alkyl.

In one or more embodiments, the C4-C18 alkyl in the C4-C18 alkyl or C4-C18 alkyl substituted by R ^1-1 is each independently C4 alkyl, C5 alkyl or C6 alkyl .

In one or more embodiments, the C4-C18 alkyl group in the C4-C18 alkyl group or the C4-C18 alkyl group substituted by R ^1-1 is each independently n-butyl, isobutyl, sec-butyl , tert-butyl, n-pentyl or n-hexyl.

In one or more embodiments, the C4-C18 alkyl group in the C4-C18 alkyl group or the C4-C18 alkyl group substituted by R ^1-1 is each independently n-butyl or n-hexyl.

In one or more embodiments, R ¹ and R ² are each independently C4-C18 alkyl.

In one or more embodiments, the ruthenium carbene compound represented by the formula 1 is any of the following structures:

In one or more embodiments, the unsaturated acid anhydride is a cyclic acid anhydride comprising the structure:

Wherein, the wavy line indicates the position where the structure is connected with the rest of the cyclic acid anhydride; preferably, the ring in the cyclic acid anhydride is a bridged ring, a spiro ring or a condensed ring, and the ring optionally contains O except for forming the acid anhydride. an additional heteroatom other than O, S and N, and the ring is optionally substituted with 1-6 substituents selected from halogen and C1-C4 alkyl.

In one or more embodiments, the ester is a monoester or a polyester, and at least one of the fatty acid chain and the fatty alcohol chain forming the ester contains a C=C double bond; preferably, the fatty acid chain and the fatty acid chain contain a C=C double bond. At least one chain in the alcohol chain contains a ring structure; preferably, the ring structure is a bridged ring, a spiro ring or a condensed ring; preferably, the ring structure is an unsaturated ring containing the C=C double bond.

In one or more embodiments, the ring in the cyclic anhydride is an unsaturated ring containing the C=C structure.

In one or more embodiments, the ring structure of the ester includes a C4-C8 cycloalkene or a C4-C8 bridged cycloalkene, such as bicyclo[2.2.1]-2-heptene and cyclohexene; preferably, the The fatty acid chain of the ester is derived from the fatty acid chain of 5-norbornene-2,3-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1-carboxylic acid and maleic acid; preferably Typically, the fatty alcohol chain of the ester is a fatty acid chain of a C1-C4 alcohol.

In one or more embodiments, the unsaturated anhydride and/or ester is selected from maleic anhydride, 5,6-dimethyl-3a,4,7,7a-tetrahydro-2-benzofuran -1,3-Dione, Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, 1,2,5,6-tetrahydrophthalic anhydride, Nadic anhydride, Methyl Nadic anhydride, Maleic anhydride, citraconic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, biphthalic anhydride, exo-norbornene dianhydride, endo-norbornene dioic anhydride, exo-furan-malon Maleic anhydride adduct, exo-cyclohexene-maleic anhydride adduct, dimethyl 5-norbornene-2,3-dicarboxylate, dimethyl 4-cyclohexene-1,2-dicarboxylate ester, one or more of methyl 3-cyclohexene-1-carboxylate and diethyl maleate.

In one or more embodiments, the liquid catalyst composition contains 0.5-50 wt%, preferably 3-40 wt%, more preferably 5-30 wt% of the ruthenium carbene catalyst, based on the total weight of the liquid catalyst composition.

In one or more embodiments, the liquid catalyst composition contains 35-99.5 wt %, preferably 75-95 wt % of the unsaturated acid anhydride and/or ester, based on the total weight of the liquid catalyst composition.

In one or more embodiments, the stabilizer is an organophosphine stabilizer and/or an elastomer.

In one or more embodiments, the organic phosphine is selected from one or more of tricyclohexylphosphine, triphenylphosphine and trihexylphosphine, more preferably tricyclohexylphosphine.

In one or more embodiments, the elastomer is selected from one or more of thermoplastic elastomer, ethylene propylene rubber, ethylene propylene diene propylene rubber, ABS, ASA and natural rubber materials, more preferably ABS.

In one or more embodiments, the liquid catalyst composition contains 0.1 to 12 wt % of the stabilizer, based on the total weight of the liquid catalyst composition.

In one or more embodiments, the stabilizer is an organic phosphine in an amount of 0.1-5 wt%.

In one or more embodiments, the stabilizer is an elastomer in an amount of 0.1-12 wt%.

In one or more embodiments, the viscosity of the liquid catalyst composition is < 450 mPa·s.

In one or more embodiments, the viscosity of the liquid catalyst composition is < 200 mPa·s.

The second aspect of the present invention provides a cyclic olefin resin composition, the cyclic olefin resin composition includes composition A and composition B, wherein, composition A contains the composition of cyclic olefin, and composition B contains any one of the embodiments herein The liquid catalyst composition.

In one or more embodiments, Composition A contains not less than 40 wt% DCPD and 0.5-60 wt% TCPD, and optionally cycloolefin compounds other than DCPD and TCPD.

In one or more embodiments, the cycloolefin compound other than DCPD and TCPD is selected from cyclooctadiene, ethylidene norbornene, methylcyclopentadiene dimer.

In one or more embodiments, the composition A also contains an antioxidant.

In one or more embodiments, the antioxidant is selected from 2,6-di-tert-butyl-p-cresol, t-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol and one or more of resorcinol.

In one or more embodiments, the mass ratio of composition A to composition B is 10:1-550:1.

In one or more embodiments, the mass ratio of composition A to composition B is 50:1-250:1.

A third aspect of the present invention provides a cyclic olefin resin material prepared from the cyclic olefin resin composition described in any one of the embodiments herein.

In one or more embodiments, the cyclic olefin resin material has a tensile strength ≥ 50 MPa, a tensile modulus ≥ 2012 MPa, and an elongation at break ≥ 5.9%.

A fourth aspect of the present invention provides a method for preparing a thermosetting cycloolefin resin, the method comprising the step of subjecting a liquid cycloolefin or a liquid cycloolefin composition to a ROMP reaction in the presence of the liquid catalyst composition described in any of the embodiments herein .

Detailed ways

In view of the above problems, the present invention directly dissolves/disperses the ruthenium carbene catalyst in an unsaturated acid anhydride containing a C=C structure and having no more than 20 carbon atoms in the molecule and/or containing a C=C structure and having no more than 20 carbon atoms in the molecule. In the ester, a stable liquid low-viscosity catalyst composition (also referred to as a catalytic system) is formed. This catalytic system has good storage stability; using this catalyst composition for ROMP reaction of liquid cycloolefin or liquid cycloolefin composition can easily realize continuous automatic production; in addition, the dispersion system used in this catalytic system will not cause The mechanical properties of the products obtained from the polymerization of cycloolefins are reduced. Moreover, in the process of preparing the catalytic system, the present invention does not need to introduce chlorinated paraffin to dissolve the catalyst, avoids the use of high-viscosity materials in the process of constructing the catalyst composition, and improves the accuracy and accuracy of material injection and mixing in the process. The operability is more conducive to the realization of continuous and automatic production process. In addition, the resin and the catalyst composition used in the present invention do not need to be compounded with the epoxy resin formulation to form a stable component and can be used alone.

Ruthenium Carbene Catalyst

Ruthenium carbene catalyst refers to a chemical compound containing ruthenium element and carbene structure, which is often used to catalyze the metathesis reaction of olefins. The ruthenium carbene catalyst suitable for the present invention can be selected from one or more of Grubbs first-generation catalysts, Grubbs second-generation catalysts and ruthenium carbene compounds represented by formula I or salts thereof.

Herein, the Grubbs first generation catalyst has the following structure:

The Grubbs second generation catalyst has the following structure:

The ruthenium carbene compound represented by the formula I can be as described in CN 202011520977.8 (the entire content of which is incorporated herein by reference). Specifically, the ruthenium carbene compound described in the formula I has the following structure:

in,

R ₁ and R ₂ are each independently C ₄ -C ₁₈ alkyl or C ₄ -C ₁₈ alkyl substituted by R _1-1 ; R _1-1 is C ₆ -C ₁₀ aryl; Cy is cyclohexyl; Mes is mesityl of the formula (the wavy line indicates the position of attachment to the rest of the compound of formula I):

In some specific embodiments, the C4-C18 alkyl group in the C4-C18 alkyl group or the C4-C18 alkyl group substituted by R ^1-1 can be independently a C4-C10 alkyl group, preferably a C4-C6 alkyl group group, such as C4 alkyl, C5 alkyl or C6 alkyl, and n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, preferably n-butyl or n-hexyl.

In some specific embodiments, in the C4-C18 alkyl substituted by R ^1-1 , the number of R ^1-1 can be 1, 2 or 3, and when it is 2 or 3, same or different.

In some specific embodiments, the C6-C10 aryl group may be phenyl or naphthyl.

In some specific embodiments, R ¹ and R ² can independently be n-butyl or n-hexyl.

In some specific embodiments, R ¹ and R ² can independently be C4-C18 alkyl.

In some having embodiments, R ¹ and R ² can be the same or different.

In some embodiments, the ruthenium carbene compound shown in formula I of the present invention can be selected from any of the following structures:

In some specific embodiments, the ruthenium carbene catalyst is the ruthenium carbene compound I-1 represented by the following structural formula of the Grubbs second-generation catalyst:

In the present invention, the liquid catalyst composition containing ruthenium carbene catalyst, based on its total weight, contains 0.5-50wt%, preferably 3-40wt%, more preferably 5-30wt% of ruthenium carbene catalyst. In some embodiments, the liquid catalyst composition contains 5-15 wt% ruthenium carbene catalyst. In some embodiments, the liquid catalyst composition contains 8-15 wt% ruthenium carbene catalyst. In some specific embodiments, the ruthenium carbene catalyst-containing liquid catalyst composition contains 5-15 wt % (eg, about 10 wt %) of the ruthenium carbene catalyst I-1. In some specific embodiments, the ruthenium carbene catalyst-containing liquid catalyst composition contains 5-15 wt% Grubbs second generation catalyst.

Unsaturated acid anhydrides with C=C structure and no more than 20 carbon atoms in the molecule and/or C=C structure and carbon number in the molecule Esters not exceeding 20

The present invention selects the unsaturated acid anhydride containing C=C structure and the carbon number in the molecule does not exceed 20 and/or the ester containing the C=C structure and the carbon number in the molecule does not exceed 20 as the dispersion system (i.e. solvent) of the ruthenium carbene catalyst, Liquid catalyst compositions of the present invention are prepared. The unsaturated acid anhydrides and esters do not have groups capable of dissociating active H ⁺ or H·, such as -OH, -COOH, etc., in the molecules of the unsaturated acid anhydrides and esters.

In the present invention, preferably, the unsaturated acid anhydride having a C=C structure and having no more than 20 carbon atoms in the molecule is a cyclic acid anhydride. The cyclic acid anhydride includes the following structure:

where the wavy line indicates where the structure is attached to the rest of the cyclic anhydride. The ring in the cyclic acid anhydride may be a bridged ring, a spiro ring or a condensed ring, and usually the number of ring atoms in the ring may be in the range of 5-15. The ring may optionally contain additional heteroatoms other than the anhydride forming O, the additional heteroatoms being selected from O, S and N. Preferably, the number of the additional heteroatoms is 1, 2 or 3. The ring may be optionally substituted, eg, with 1-6 substituents selected from halogen (including F, Cl, Br and I) and C1-C4 alkyl. Preferably, the ring is an unsaturated ring containing the C═C structure. Exemplary unsaturated anhydrides include, but are not limited to, maleic anhydride, 5,6-dimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione, bicyclo[ 2.2.1] Hept-5-ene-2,3-dicarboxylic acid anhydride, 1,2,5,6-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, citraconic anhydride, o-phthalic anhydride Dicarboxylic anhydride, tetrachlorophthalic anhydride, biphenyl anhydride, exo-norbornene dianhydride, endo-norbornene dianhydride, exo-furan-maleic anhydride adduct and exo-cyclic Hexene-maleic anhydride adduct, etc.

In the present invention, esters are formed from fatty acids and fatty alcohols, and may be monoesters or polyesters. Monoesters are esters of monocarboxylic acids and fatty alcohols, or esters of monohydric alcohols and carboxylic acids. The polybasic ester can be an ester formed by a polybasic organic acid and a fatty alcohol, or an ester formed by a polybasic alcohol and a fatty acid, and has two or more ester groups [-C(O)-O-] in its molecular structure. In the ester of the present invention, at least one of the fatty acid chain and the fatty alcohol chain contains a C=C double bond. The number of carbon atoms in the fatty acid chain and the number of carbon atoms in the fatty alcohol chain are such that the total number of carbon atoms in the ester does not exceed 20. In a preferred embodiment, at least one of the fatty acid chain and the fatty alcohol chain contains a ring structure, and preferably the C=C double bond is located on this ring structure. The ring structure may be bridged, spiro or fused, and may optionally contain heteroatoms selected from O, N and S, and the number of heteroatoms may be 1-3. The number of ring atoms of the ring structure may be 3-10. Exemplary ring structures include C4-C8 cycloalkenes or C4-C8 bridged cycloalkenes, such as bicyclo[2.2.1]-2-heptene and cyclohexene. Exemplary ester fatty acid chains include, but are not limited to, from 5-norbornene-2,3-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1-carboxylic acid, and maleic acid acid chain of fatty acids. Exemplary fatty alcohol chains include, but are not limited to, C1-C4 alcohols such as methanol, ethanol, and the like. In some embodiments, exemplary esters include dimethyl 5-norbornene-2,3-dicarboxylate, dimethyl 4-cyclohexene-1,2-dicarboxylate, 3-cyclohexene-1 - one or more of methyl formate and diethyl maleate.

In the present invention, the content of the unsaturated acid anhydride and/or ester in the liquid catalyst composition of the present invention may be 35-99.5 wt %, preferably 70-95 wt %. In some embodiments, the content of the unsaturated acid anhydride and/or ester in the liquid catalyst composition of the present invention is 85-95 wt%.

In some specific embodiments, the ruthenium carbene catalyst-containing liquid catalyst composition contains 80-95 wt% nadic anhydride, eg, about 90 wt% nadic anhydride. In some specific embodiments, the ruthenium carbene catalyst-containing liquid catalyst composition contains 85-95 wt% methylnadic anhydride, eg, about 90 wt% methylnadic anhydride. In some specific embodiments, the ruthenium carbene catalyst-containing liquid catalyst composition contains a mixture of 10-20 wt% nadic anhydride and 60-85 wt% methyl nadic anhydride, eg, about 17 wt% nadic anhydride and about 70 wt% mixture of methyl nadic anhydride. In other specific embodiments, the liquid catalyst composition containing ruthenium carbene catalyst contains 5-20wt% maleic anhydride, 40-70wt% 1,2,5,6-tetrahydrophthalic anhydride and 15-20wt% A mixture of dimethyl 5-norbornene-2,3-dicarboxylate, such as about 8.8 wt % maleic anhydride, about 59.84 wt % 1,2,5,6-tetrahydrophthalic anhydride and about 17.6 wt % A mixture of dimethyl 5-norbornene-2,3-dicarboxylate; or about 18 wt % maleic anhydride, about 50.4 wt % 1,2,5,6-tetrahydrophthalic anhydride and about 18 wt % 5-nor A mixture of dimethylbornene-2,3-dicarboxylate.

In the present invention, there are two reasons for directly dissolving/dispersing the ruthenium carbene catalyst by selecting an unsaturated acid anhydride containing a C=C structure and having no more than 20 carbon atoms in the molecule and/or an ester containing a C=C structure and having no more than 20 carbon atoms in the molecule. :

First, the present inventors found that if the solvent/dispersant used in the catalytic system is too polar, it will lead to a sharp drop in the catalyst activity. Therefore, choosing acid anhydrides and esters with moderate polarity as the solvent/dispersant of the catalytic system can ensure that the catalyst has good catalytic activity for cycloolefins on the premise of fully dissolving/dispersing the catalyst. In the present invention, the moderate polarity means that there is no group (such as -OH, -COOH, etc.) that is easy to dissociate from active H ⁺ or H in the molecular structure in the system, such as the unsaturated used in the present invention. Substances such as acid anhydrides and esters will not spontaneously dissociate active H ⁺ or H · without external stimulation.

Secondly, when using ruthenium carbene catalysts to cure cycloolefins or their compositions (especially cycloolefin composition systems based on DCPD, TCPD and their derivatives), the non-reactive solvent/dispersant in the system will intensify The surface flow mark phenomenon of the product increases the probability of defects inside the material during the curing process. When constructing the catalytic system of the present invention, the used dispersion system and the dissolved catalyst have reactivity under certain circumstances, which will help to overcome the aforementioned adverse effects on product performance when using common solvents. Therefore, it is possible to use unsaturated acid anhydrides containing C=C structure in the molecular structure and no more than 20 carbon atoms in the molecule and/or esters containing C═C structure and no more than 20 carbon atoms in the molecule as the solvent/dispersant of the catalytic system. The aforementioned requirements are better met.

optional stabilizer

In some embodiments, the present inventors have found that the addition of stabilizers can inhibit or reduce the slow reaction of ruthenium carbene catalysts with the ruthenium carbene catalyst at room temperature due to the presence of the C=C structure in the acid anhydride and/or ester or by external accidental factors Oligomerization caused by stimulation, and oligomerization caused by localized areas of excessive concentration or rapid bottoming in the initial stage of mixing when powder/colloidal catalysts are formulated into low-viscosity solvents/dispersants . For this reason, before mixing the ruthenium carbene catalyst into the dispersion system, an appropriate amount of stabilizer can be added to the dispersion system of the present invention, and the processability in the mixing process can be improved by adjusting the viscosity of the system (such as ≤250cP, 25°C). Accordingly, in these embodiments, the liquid catalyst compositions of the present invention may also contain appropriate amounts of stabilizers.

In the present invention, suitable stabilizers include, but are not limited to, organic phosphine stabilizers and elastomers. Exemplary organophosphines include, but are not limited to, one or more of tricyclohexylphosphine, triphenylphosphine, trihexylphosphine, and phosphine compounds having similar structures, a preferred organophosphine is tricyclohexylphosphine. Exemplary elastomers include, but are not limited to, one or more of thermoplastic elastomer (POE), ethylene propylene rubber, ethylene propylene diene propylene rubber (EPDM), ABS, ASA, and natural rubber, among other materials. The preferred elastomer is ABS. In particular, when the solubility of the ruthenium carbene catalyst (such as the second-generation Grubbs catalyst) in the dispersion system disclosed in the present invention is relatively low and the dissolution rate is relatively slow, adding an appropriate amount of elastomer to the liquid catalyst composition of the present invention has It helps to improve its solubility and dissolution rate, so as to obtain a stable colloidal dispersion system and prevent the catalyst from precipitation and sedimentation from the system.

When added, the stabilizer may be present in an amount of 0.1 to 12 wt% based on the total weight of the liquid catalyst composition. In some embodiments, organophosphorus is used as a stabilizer in an amount of 0.1-5 wt%, such as 1-4 wt%, in the liquid catalyst composition. In some embodiments, an elastomer is used as a stabilizer, which may be present in the liquid catalyst composition in an amount of 0.1-12 wt%, such as 1-5 wt%. In some embodiments, ABS is used as a stabilizer in an amount of 1-3 wt% in the liquid catalyst composition.

liquid catalyst composition

The liquid catalyst composition of the present invention contains a ruthenium carbene catalyst, an unsaturated acid anhydride containing a C=C structure and no more than 20 carbon atoms in the molecule, and/or an ester containing a C═C structure and no more than 20 carbon atoms in the molecule, and optionally stabilizer. The liquid catalyst composition has low viscosity and is stable, and can be used for ROMP reaction of liquid cyclic olefin or liquid cyclic olefin composition to realize continuous automatic production.

In some embodiments, the liquid catalyst composition of the present invention may contain 35-99.5 wt %, preferably 75-95 wt % of said unsaturated anhydride and/or ester, 3-40 wt %, preferably 5-30 wt % of said unsaturated acid anhydride and/or ester Ruthenium carbene catalyst and optional stabilizer.

In some preferred embodiments, the liquid catalyst compositions of the present invention contain 85-95 wt % (eg, 90 wt %) of Nadic anhydride and 5-15 wt % (eg, about 10 wt %) of Ruthenium Carbene Catalyst I-1. In other preferred embodiments, the liquid catalyst composition of the present invention contains 15-25wt% (eg about 20wt%) of nadic anhydride, 65-75wt% (eg 70wt%) of methyl nadic anhydride and 5-15wt% % (eg, about 10 wt%) of Ruthenium Carbene Catalyst I-1. In some other preferred embodiments, the liquid catalyst composition of the present invention contains 15-20wt% (eg about 17wt%) nadic anhydride, 65-75wt% (eg about 70wt%) methyl nadic anhydride, 5-15wt% % (eg, about 10 wt%) of ruthenium carbene catalyst I-1 and 1-5 wt% (eg, about 3 wt%) of tricyclohexylphosphine.

Meanwhile, the liquid catalyst composition of the present invention can also be prepared from Grubbs second-generation catalyst and catalyst system dispersion. In some preferred embodiments, based on the total weight of the catalytic system dispersion, containing 8-12 wt % (eg about 10 wt %) maleic anhydride, 65-70 wt % (eg about 68 wt %) 1,2,5,6- Tetrahydrophthalic anhydride, 18-22 wt % (eg, about 20 wt %) of dimethyl 5-norbornene-2,3-dicarboxylate, 1-3 wt % (eg, about 2 wt %) of tricyclohexylphosphine. In some other preferred embodiments, based on the total weight of the catalytic system dispersion, containing 18-22wt% (eg about 20wt%) of maleic anhydride, 55-60wt% (eg about 56wt%) of 1,2,5,6 - Tetrahydrophthalic anhydride, 18-22wt% (eg about 20wt%) of dimethyl 5-norbornene-2,3-dicarboxylate, 1-3wt% (eg about 2wt%) of tricyclohexylphosphine, 1-3wt% (eg about 2 wt%) ABS. Wherein, the mass ratio of Grubbs second-generation catalyst and dispersion system (containing the unsaturated acid anhydride and/or ester and optional stabilizer of the present invention) is 5-20:80-95.

It should be noted that in the liquid catalyst composition configuration process, the ruthenium carbene catalyst can be pre-dissolved in a small amount of traditional low-viscosity and low-boiling solvents, such as benzene, toluene, xylene, petroleum ether, etc., and then mixed with the solvent/ The dispersant is mixed, and after the mixing is uniform, a pump of a certain shape is used to remove the low-boiling traditional solvent from the catalytic system, and the effect described in the present invention can also be achieved.

In some embodiments, the viscosity (25° C.) of the liquid catalyst composition of the present invention is ≤450 mPa·s, preferably ≤300 mPa·s, more preferably ≤150 mPa·s. In some embodiments, the viscosity (25° C.) of the liquid catalyst composition of the present invention is less than or equal to 50 mPa·s.

resin composition

The present invention provides a cyclic olefin resin composition, which comprises composition A and composition B, wherein: composition A contains cyclic olefin, and composition B contains the liquid catalyst composition described herein.

Herein, the cycloolefin may be a cycloolefin known in the art for preparing cycloolefin resins, including but not limited to DCPD, TCPD, cyclooctadiene, ethylidene norbornene, and methylcyclopentadiene dimers one or more of. Preferably, the composition A of the present invention contains DCPD and TCPD, wherein, based on the total weight of the composition A, the content of DCPD is greater than or equal to 40 wt %, and the content of TCPD can be 0.5-60 wt %. In addition to DCPD and TCPD, composition A may also contain other cycloolefin monomers known in the art that can be used to prepare cycloolefin resins, including but not limited to cyclooctadiene, ethylidene norbornene, and methylcyclopentadiene one or more of the dimers. Preferably, the cyclic olefin is a liquid cyclic olefin at normal temperature (25°C).

In some embodiments, an antioxidant may also be added to Composition A. Antioxidants known in the art for preparing resins, especially cycloolefin resins, can be used in the present invention. Exemplary antioxidants include, but are not limited to, phenolic and/or phenyl ether antioxidants such as 2,6-di-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, One or more of phenolic or phenyl ether substances such as tert-butyl-p-cresol and resorcinol. The amount of the antioxidant in the composition A can be the conventional amount in the art, and an exemplary amount is 0.1-2 wt% based on the total weight of the composition A.

In the resin composition of the present invention, the mass ratio of composition A to composition B may be 10:1-550:1. In some embodiments, the mass ratio of Composition A to Composition B is 50:1 to 250:1.

Cycloolefin resin material and its preparation

The present invention also provides a cyclic olefin resin material, which is prepared from the above-mentioned cyclic olefin resin composition. In some embodiments, the cyclic olefin resin material has a tensile strength > 50 MPa, a tensile modulus > 2000 MPa, and an elongation at break > 5.5%. In a preferred embodiment, the tensile modulus of the cyclic olefin resin material is ≥ 2010 MPa, more preferably ≥ 2020 MPa. In a preferred embodiment, the elongation at break of the cyclic olefin resin material is ≥ 6.0%, more preferably ≥ 6.5%.

The cyclic olefin resin material can be prepared using the liquid catalyst composition disclosed in the present invention by methods well known in the art. An exemplary preparation method includes introducing the above-mentioned composition A and composition B into a mold for reaction, and the temperature of the mold can be controlled in the range of 40-140°C, preferably 60-100°C. An appropriate reaction time can be selected according to the amount of reactants. Exemplary reaction times (curing times) may be 0.1-8 hours. Compositions A and B can be injected into the mold using RIM equipment. As mentioned above, the mass ratio of composition A and composition B may be 10:1-550:1, preferably 50:1-250:1.

The invention will hereinafter be illustrated by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the invention. The methods, reagents and materials used in the examples, unless otherwise specified, are conventional methods, reagents and materials in the art. The raw material compounds in the examples can be purchased from commercial sources.

The methods for measuring the tensile strength, tensile modulus and elongation at break of the cyclic olefin resin material of the present invention are all carried out in accordance with GB/T 2567-2008. The specifications of the cast resin panels can meet the above test standards.

Example 1

1. Preparation of cycloolefin composition (composition A): add 90 parts by mass of DCPD and 10 parts by mass of TCPD in the stirred tank, after the atmosphere in the replacement tank is high-purity nitrogen, be heated to 60° C., stirred for 2 hours, and the heating is completed. After that, the material is sealed and discharged, and the product is stored under nitrogen sealing in the raw material barrel.

2. the preparation of liquid catalyst composition (composition B): under the protection of dry nitrogen atmosphere, add 90 parts by mass of Nadic anhydride in the dry glass still, then add 10 parts of ruthenium carbene catalysts I- 1. Stir at 25°C for 2 hours (stirring speed is 600 rpm). After the stirring, the material was sealed and discharged, and the obtained material (viscosity <10mPa·s, 25°C) was stored in a raw material barrel under nitrogen sealing.

3. Preparation of polycyclic olefin resin material: package the prepared components A and B into the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold. The mold temperature was 80°C and the curing time was 3 hours. The resulting material had a tensile strength of 51 MPa, a tensile modulus of 2012 MPa, and an elongation at break of 6.9%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.13 mm (resin sheet thickness was 4 mm).

Example 2

1. Preparation of cycloolefin composition (component A): 89.5 parts by mass of DCPD and 10 parts by mass of TCPD were added to the stirred tank, and after the atmosphere in the tank was replaced with high-purity nitrogen, the temperature was raised to 60° C. and stirred for 2 hours. After the heating was completed, it was cooled to room temperature, 0.5 parts by mass of 2,6-di-tert-butyl-p-cresol (antioxidant, antioxidant) was added, and the mixture was stirred for 0.5 hours. After the mixing is completed, the material is sealed and discharged, and the product is stored in a nitrogen-sealed storage tank.

2. Preparation of the liquid catalyst composition (component B): under the protection of a dry nitrogen atmosphere, add 20 parts by mass of Nadic anhydride and 70 parts by mass of methyl Nadic anhydride to a dry glass kettle, and then under stirring conditions 10 parts by mass of ruthenium carbene catalyst I-1 was added, and the mixture was stirred at 25° C. for 2 hours (stirring speed was 600 rpm). After the stirring, the material was sealed and discharged, and the obtained material (viscosity <10mPa·s, 25°C) was stored in a raw material barrel under nitrogen sealing.

3. Preparation of polycyclic olefin resin material: package the prepared components A and B into the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold. The mold temperature was 80°C and the curing time was 3 hours. The resulting material had a tensile strength of 52 MPa, a tensile modulus of 2024 MPa, and an elongation at break of 7.0%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.13 mm (resin sheet thickness was 4 mm).

Example 3

1. Preparation of cycloolefin composition (component A): 90 parts by mass of DCPD and 9.5 parts by mass of TCPD were added to the stirred tank, and after the atmosphere in the tank was replaced with high-purity nitrogen, the temperature was raised to 60° C. and stirred for 2 hours. After the heating was completed, it was cooled to room temperature, 0.5 parts by mass of 2,6-di-tert-butyl-p-cresol was added, and the mixture was stirred for 0.5 hours. After the mixing is completed, the material is sealed and discharged, and the product is stored in a nitrogen-sealed storage tank.

2. Preparation of the liquid catalyst composition (component B): under the protection of a dry nitrogen atmosphere, add 17 parts by mass of Nadic anhydride and 70 parts by mass of methyl Nadic anhydride to a dry glass kettle, and then under stirring conditions 10 parts by mass of ruthenium carbene catalyst I-1 was added, and the mixture was stirred at 25° C. for 2 hours (stirring speed was 600 rpm), and then 3 parts by mass of tricyclohexylphosphine was added to the glass kettle. After the stirring, the material was sealed and discharged, and the obtained material (viscosity <10mPa·s, 25°C) was stored in a raw material barrel under nitrogen sealing.

3. Preparation of polycyclic olefin resin material: package the prepared components A and B into the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold. The mold temperature was 80°C and the curing time was 3 hours. The resulting material had a tensile strength of 52 MPa, a tensile modulus of 2026 MPa, and an elongation at break of 7.1%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.14 mm (resin sheet thickness was 4 mm).

Example 4

1. Preparation of cycloolefin composition (component A): add 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer in the stirred tank, and the atmosphere in the replacement tank is high-purity nitrogen Then, the temperature was raised to 60° C. and stirred for 2 hours. After the reaction was completed, the material was sealed and discharged, and the product was stored in a raw material barrel under nitrogen sealing.

2. The preparation of liquid catalyst composition (component B): under the protection of dry nitrogen atmosphere, add 90 parts by mass of methyl nadic anhydride to the dry glass still, then add 10 parts of ruthenium carbene catalysts under stirring conditions I-1, stirred at 25°C for 2 hours (stirring speed: 600 rpm). After the stirring, the material was sealed and discharged, and the obtained material (viscosity <10mPa·s, 25°C) was stored in a raw material barrel under nitrogen sealing.

3. Preparation of polycyclic olefin resin material: package the prepared components A and B into the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold. The mold temperature was 80°C and the curing time was 3 hours. The resulting material had a tensile strength of 52 MPa, a tensile modulus of 2044 MPa, and an elongation at break of 7.3%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.14 mm (resin sheet thickness was 4 mm).

Example 5

1. Preparation of cycloolefin composition (component A): add 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer in the stirred tank, and the atmosphere in the replacement tank is high-purity nitrogen Then, the temperature was raised to 60° C. and stirred for 2 hours. After the reaction was completed, the material was sealed and discharged, and the product was stored in a raw material barrel under nitrogen sealing.

2. Preparation of liquid catalyst composition dispersion: under the protection of a dry nitrogen atmosphere, add 10 parts by mass of maleic anhydride, 68 parts by mass of 1,2,5,6-tetrahydrophthalic anhydride, 20 parts by mass into a dry glass kettle Dimethyl 5-norbornene-2,3-dicarboxylate and 2 parts by mass of tricyclohexylphosphine were fully stirred, then heated to 60°C, continued to stir at this temperature for 2 hours (stirring speed was 600 rpm), and thoroughly mixed After that, it was cooled to room temperature.

3. the preparation of liquid catalyst composition (component B): 12 mass parts of Grubbs second-generation catalysts were added quickly under the protection of dry nitrogen in the reactor containing 88 mass parts of prepared dispersions, vigorously stirred ( 600rpm) for 1 hour. During the stirring process, the temperature of the material was controlled at 10°C. After the stirring, the material was sealed and discharged, and the obtained material (viscosity <10mPa·s, 25°C) was stored in a raw material barrel under nitrogen sealing.

4. Preparation of polycyclic olefin resin material: The prepared A and B components are packaged into the corresponding material tanks respectively, and the A and B streams are mixed at a mass ratio of 150:1 using special RIM equipment and injected into the mold. The mold temperature was 80°C and the curing time was 3 hours. The resulting material had a tensile strength of 52 MPa, a tensile modulus of 2052 MPa, and an elongation at break of 5.9%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.12 mm (resin sheet thickness was 4 mm).

Example 6

1. Preparation of cycloolefin composition (component A): add 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer in the stirred tank, and the atmosphere in the replacement tank is high-purity nitrogen Then, the temperature was raised to 60° C. and stirred for 2 hours. After the reaction was completed, the material was sealed and discharged, and the product was stored in a raw material barrel under nitrogen sealing.

2. Preparation of liquid catalyst composition dispersion: under the protection of a dry nitrogen atmosphere, add 20 parts by mass of maleic anhydride, 56 parts by mass of 1,2,5,6-tetrahydrophthalic anhydride, 20 parts by mass into a dry glass kettle Dimethyl 5-norbornene-2,3-dicarboxylate, 2 parts by mass of tricyclohexylphosphine and 2 parts by mass of ABS, fully stirred, heated to 80°C, and continued to stir at this temperature for 12 hours (stirring speed was 600 rpm), mixed well, and cooled to room temperature (viscosity: 150 mPa·s, 25° C.).

3. the preparation of liquid catalyst composition (component B): 10 mass parts of Grubbs second-generation catalysts were added quickly under the protection of dry nitrogen in the reactor containing 90 mass parts of prepared dispersions, vigorously stirred ( 600rpm) for 1 hour. During the stirring process, the temperature of the material was controlled at 10°C. After stirring, the material was sealed and discharged, and the obtained material (viscosity: 150 mPa·s, 25° C.) was stored in a raw material barrel under nitrogen sealing.

4. Preparation of polycyclic olefin resin material: package the prepared components A and B into the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold , the mold temperature is 80 °C, and the curing time is 3 hours. The resulting material had a tensile strength of 53 MPa, a tensile modulus of 2082 MPa, and an elongation at break of 6.9%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.10 mm (resin sheet thickness 4 mm).

Comparative Example 1 (with DCPD single component as component A)

1. the preparation of liquid catalyst composition (component B): under the protection of dry nitrogen atmosphere, in dry glass still, add 90 parts by mass of Nadic acid anhydride, then add 10 parts of ruthenium carbene catalysts 1- 1. Stir at 25°C for 2 hours. After the stirring, the material was sealed and discharged, and the obtained material (viscosity <10mPa·s, 25°C) was stored in a raw material barrel under nitrogen sealing.

2. Preparation of polycyclic olefin resin material: take DCPD as component A, package components A and B into corresponding tanks, and keep the temperature at 35 °C for 1 hour. After mixing in a mass ratio of 150:1, it was injected into the mold, the mold temperature was 80 °C, and the curing time was 3 hours. The resulting material had a tensile strength of 48 MPa, a tensile modulus of 1851 MPa, and an elongation at break of 5.4%.

Comparative example 2 (with toluene as solvent)

1. Preparation of cycloolefin composition (component A): add 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer in the stirred tank, and the atmosphere in the replacement tank is high-purity nitrogen Then, the temperature was raised to 60° C. and stirred for 2 hours. After the reaction was completed, the material was sealed and discharged, and the product was stored in a raw material barrel under nitrogen sealing.

2. Preparation of the liquid catalyst composition (component B): Before proceeding with material preparation, 10 parts by mass of Grubbs second-generation catalyst was dissolved in 90 parts by mass of toluene.

3. Preparation of polycyclic olefin resin material: package the prepared components A and B into the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold. The mold temperature was 80°C and the curing time was 3 hours. The resulting material had a tensile strength of 50 MPa, a tensile modulus of 1998 MPa, and an elongation at break of 5.8%. One side of the obtained sample was smooth, while the other side had numerous grooves with an average depth of 0.25 mm (thickness 4 mm).

Example 7

1. Component A and Component B were prepared according to Example 3 above. Among them, component B was formulated 6 months in advance and stored at room temperature.

2. Preparation of polycyclic olefin resin material: package the freshly prepared component A and the component B that has been stored for 6 months into the corresponding material tanks respectively, and use special RIM equipment to divide the two streams of A and B according to the mass of 150:1 After mixing, it was poured into a mold, the mold temperature was 80°C, and the curing time was 3 hours. The resulting material had a tensile strength of 52 MPa, a tensile modulus of 2012 MPa, and an elongation at break of 7.1%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.13 mm (resin sheet thickness was 4 mm).

Comparative Example 3

1. According to the method in Comparative Example 2, prepare component A and component B. Among them, component B was prepared 24 hours in advance and stored at room temperature.

2. Package component A and component B placed for 24 hours in the corresponding material tanks respectively, and use special RIM equipment to mix the two streams of A and B at a mass ratio of 150:1 and inject them into the mold. The mold temperature is 80 ℃, the curing time is 3 hours. After the mold was opened, it was found that the material was not fully cured and was gel-like.

Example 8

1. Component A and Component B were prepared according to the aforementioned Example 5, respectively. Among them, component B was formulated 6 months in advance and stored at room temperature.

2. Preparation of polycyclic olefin resin material: package the freshly prepared component A and the component B stored for 6 months (viscosity <10mPa·s, 25°C) into the corresponding material tanks respectively, and use special RIM equipment to seal A. The two streams of B and B are mixed in a mass ratio of 150:1 and injected into the mold, the mold temperature is 80 °C, and the curing time is 3 hours. The resulting material had a tensile strength of 52 MPa, a tensile modulus of 2049 MPa, and an elongation at break of 6.1%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.12 mm (resin sheet thickness was 4 mm).

Example 9

1. Component A and Component B were prepared according to the aforementioned Example 6, respectively. Among them, component B was formulated 6 months in advance and stored at room temperature.

2. Preparation of polycyclic olefin resin material: package the freshly prepared component A and the component B (viscosity: 152mPa·s, 25°C) that have been stored for 6 months into the corresponding material tanks respectively, and use special RIM equipment to put A The two streams of B and B are mixed in a mass ratio of 150:1 and injected into the mold, the mold temperature is 80 °C, and the curing time is 3 hours. The resulting material had a tensile strength of 53 MPa, a tensile modulus of 2075 MPa, and an elongation at break of 7.3%. One side of the obtained resin sheet was smooth, and the other side had a few flow marks, and the average depth of flow marks was 0.09 mm (resin sheet thickness was 4 mm).

The comparison between Examples 1 and 4 and Comparative Example 1 shows that when TCPD is added to component A or TCPD and the third cycloolefin monomer are added at the same time, the tensile strength and tensile modulus of the prepared resin materials can be improved. performance; through the comparison of Example 5 and Comparative Example 2, it can be found that when the same cyclic olefin composition is cured, using the catalyst composition disclosed in the present invention compared with the toluene solution of the traditional Grubbs second-generation catalyst, The resulting resin product has higher tensile modulus and tensile strength. From the comparison of Example 3, Example 7 and Comparative Examples 2-3, it can be seen that the catalyst system for the polymerization of liquid cyclic olefin compositions disclosed in the present invention has good storage stability, and can overcome the traditional catalyst solution system in The problem of easy deactivation during storage. The storage stability of the catalytic system disclosed in the present invention is further demonstrated by comparing the results of Examples 5 and 6 with Examples 8 and 9. Meanwhile, the comparison of the results of Examples 1-6 and Comparative Example 2 also shows that the use of the catalyst composition disclosed in the present invention can effectively improve the surface flow mark problem of the molding material.

Claims (17)

1. a liquid catalyst composition containing ruthenium carbene catalyst is characterized in that, this liquid catalyst composition contains ruthenium carbene catalyst, solvent and optional stabilizer, wherein, described solvent contains C=C structure and intramolecular Unsaturated acid anhydrides with no more than 20 carbon atoms and/or esters with C=C structure and no more than 20 carbon atoms in the molecule. 2. liquid catalyst composition as claimed in claim 1 is characterized in that, described ruthenium carbene catalyst is selected from:

And the ruthenium carbene compound or its salt shown in following formula I:

In the formula, R ¹ and R ² are each independently C4-C18 alkyl or C4-C18 alkyl substituted by R ^1-1 ; R ^1-1 is C6-C10 aryl; Mes is mesityl; Cy for cyclohexyl. 3. The liquid catalyst composition of claim 2, wherein The C4-C18 alkyl group in the C4-C18 alkyl group or the C4-C18 alkyl group substituted by R ^1-1 can be independently a C4-C10 alkyl group; And/or, in the C4-C18 alkyl group substituted by R ^1-1 , the number of R ^1-1 is 1, 2 or 3, when it is 2 or 3, R ^1-1 is the same or different; And/or, the C6-C10 aryl group is phenyl or naphthyl; And/or, the R ¹ and R ² are the same or different. 4. The liquid catalyst composition of claim 3, wherein The C4-C18 alkyl group in the C4-C18 alkyl group or the C4-C18 alkyl group substituted by R ^1-1 is independently a C4-C6 alkyl group, such as a C4 alkyl group, a C5 alkyl group or a C6 alkyl group, and Such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, preferably n-butyl or n-hexyl; And/or, R ¹ and R ² are independently C4-C18 alkyl. 5. liquid catalyst composition as described in claim 2, is characterized in that, the ruthenium carbene compound shown in described formula I is following any structure:

6. The liquid catalyst composition of claim 1, wherein Described unsaturated acid anhydride is cyclic acid anhydride, and it comprises following structure:

Wherein, the wavy line indicates the position where the structure is connected to the rest of the cyclic acid anhydride; preferably, the ring in the cyclic acid anhydride is a bridged ring, a spiro ring or a condensed ring, and the ring optionally contains O except for forming the acid anhydride. an additional heteroatom other than O, S and N, and the ring is optionally substituted with 1-6 substituents selected from halogen and C1-C4 alkyl; The ester is a monoester or a polyester, and at least one chain in the fatty acid chain and the fatty alcohol chain forming the ester contains a C=C double bond; preferably, at least one chain in the fatty acid chain and the fatty alcohol chain contains a ring structure ; preferably, the ring structure is a bridged ring, a spiro ring or a condensed ring; preferably, the ring structure is an unsaturated ring containing the C=C double bond. 7. The liquid catalyst composition of claim 6, wherein The ring in the cyclic acid anhydride is an unsaturated ring containing the C=C structure; The ring structure of the ester includes a C4-C8 cycloalkene or a C4-C8 bridged cyclic alkene, such as bicyclo[2.2.1]-2-heptene and cyclohexene; preferably, the fatty acid chain of the ester is derived from 5-nor Fatty acid chains of bornene-2,3-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1-carboxylic acid and maleic acid; preferably, the fatty alcohol chains of the esters is the fatty acid chain of C1-C4 alcohol; Preferably, the unsaturated anhydride and/or ester is selected from maleic anhydride, 5,6-dimethyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-di Ketone, Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, 1,2,5,6-tetrahydrophthalic anhydride, Nadic anhydride, Methyl Nadic anhydride, Maleic anhydride, citracone Acid anhydride, phthalic anhydride, tetrachlorophthalic anhydride, biphenyl anhydride, exo-norbornene dianhydride, endo-norbornene dianhydride, exo-furan-maleic anhydride adduct, Exo-cyclohexene-maleic anhydride adduct, dimethyl 5-norbornene-2,3-dicarboxylate, dimethyl 4-cyclohexene-1,2-dicarboxylate, 3-cyclohexyl One or more of methyl alkene-1-carboxylate and diethyl maleate. 8. The liquid catalyst composition of claim 1, wherein Based on the total weight of the liquid catalyst composition, the liquid catalyst composition contains 0.5-50 wt %, preferably 3-40 wt %, more preferably 5-30 wt % of a ruthenium carbene catalyst; and/or The liquid catalyst composition contains 35-99.5 wt %, preferably 75-95 wt % of the unsaturated acid anhydride and/or ester, based on the total weight of the liquid catalyst composition. 9. The liquid catalyst composition of claim 1, wherein the stabilizer is an organic phosphine stabilizer and/or an elastomer; Preferably, the organic phosphine is selected from one or more of tricyclohexylphosphine, triphenylphosphine and trihexylphosphine, more preferably tricyclohexylphosphine; Preferably, the elastomer is selected from one or more of thermoplastic elastomers, ethylene-propylene rubber, ethylene-propylene-diene rubber, ABS, ASA and natural rubber materials, more preferably ABS. 10. The liquid catalyst composition according to claim 1 or 9, characterized in that, based on the total weight of the liquid catalyst composition, the liquid catalyst composition contains 0.1-12 wt% of a stabilizer; Preferably, the stabilizer is an organic phosphine, and its content is 0.1-5wt%; Preferably, the stabilizer is an elastomer, and its content is 0.1-12 wt%. 11. The liquid catalyst system composition according to claim 1, wherein the viscosity of the liquid catalyst composition is ≤450 mPa·s, preferably ≤200 mPa·s. 12. A cyclic olefin resin composition, characterized in that, the cyclic olefin resin composition comprises: Composition A: a cyclic olefin-containing composition; Composition B: comprising the liquid catalyst composition of any one of claims 1-11. 13. The cyclic olefin resin composition of claim 12, wherein composition A contains not less than 40 wt % of DCPD and 0.5-60 wt % of TCPD, and optionally cyclic olefins other than DCPD and TCPD compound; preferably, the cycloolefin compound is selected from cyclooctadiene, ethylidene norbornene, and methylcyclopentadiene dimer. 14. The cycloolefin resin composition according to any one of claims 12-13, wherein the composition A further contains an antioxidant; preferably, the antioxidant is phenol and/or phenylene ether Antioxidants, preferably one selected from the group consisting of 2,6-di-tert-butyl-p-cresol, t-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol and resorcinol one or more. 15. The cycloolefin resin composition according to any one of claims 12-14, wherein the mass ratio of the composition A to the composition B is 10:1-550:1, preferably 50:1 -250:1. 16. A cyclic olefin resin material prepared from the cyclic olefin resin composition according to any one of claims 12-15; preferably, the cyclic olefin resin material has a tensile strength≥50MPa, a tensile Modulus ≥ 2000MPa, elongation at break ≥ 5.5%. 17. A method for preparing a thermosetting cyclic olefin resin, wherein the method comprises treating a liquid cyclic olefin or a liquid cyclic olefin composition in the presence of the liquid catalyst composition according to any one of claims 1-11 Steps to perform the ROMP reaction.