A resin composition of thermosetting cyclic olefin material and use thereof

Abstract

The application discloses a resin composition of thermosetting cycloolefin material and application thereof. Specifically disclosed is a resin composition which comprises component A and component B, wherein the component A comprises a cycloolefin, and the component B comprises a ruthenium carbene compound shown in a formula LG. The resin composition disclosed by the application can be used for producing high-performance cycloolefin polymers, has low cost, and has wide application prospect.

Description

Technical Field

[0001] This invention relates to a resin composition for thermosetting cyclic olefin materials and its applications. Background Technology

[0002] Ruthenium carbene catalysts exhibit excellent performance in ring-opening metathesis polymerization (ROMP) of monomers or compositions containing dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), and other cyclic olefins via reaction injection molding (RIM) and resin die casting (RTM). These catalysts also possess good resistance to water and oxygen, and require relatively low-requirement production equipment. However, since commonly used ruthenium carbene catalysts or their compositions are generally solids, they are difficult to use directly in continuous production processes.

[0003] Furthermore, such catalysts exhibit poor solubility in cyclic olefins, such as DCPD, and their compositions, and show strong reactivity when mixed with these substances. Therefore, in practical applications, solvents with sufficient solubility for ruthenium carbene catalysts that do not undergo vigorous polymerization reactions are commonly used to prepare the catalyst into a solution. This solution further increases the cost of using ruthenium carbene catalysts, increases volatile organic compound (VOC) emissions during production, and easily leads to catalyst deactivation, formulation compatibility issues, and product surface residue problems. Traditional production processes have introduced a series of product quality and cost problems due to the use of solvents. CN 112547126 A discloses a ruthenium carbene compound composition, which can solve the above problems to some extent. However, this compound needs to be dissolved in chlorinated paraffin to be effective. When used alone, it cannot be effectively dispersed and dissolved in cyclic olefin monomer compositions with DCPD as the main component. During dispersion, the catalyst particles are prone to explosive polymerization. Therefore, it is essential to develop a stable ruthenium carbene compound catalyst that can be in liquid form.

[0004] In addition, existing technologies typically use cyclic olefins such as DCPD, TCPD, ethylene norbornene, or combinations thereof to produce cyclic olefin polymer materials. The resulting materials have relatively low strength and modulus (test standard: GB / T2567), and there is still room for further improvement in performance. Summary of the Invention

[0005] The technical problem this invention aims to solve is to overcome the shortcomings of existing catalysts for producing cyclic olefin polymers, such as poor solubility and poor stability. To this end, this invention provides a resin composition for thermosetting cyclic olefin materials and its applications. The composition provided by this invention exhibits good performance and low cost in producing cyclic olefin polymers, and has broad application prospects.

[0006] This invention provides a resin composition comprising component A and component B;

[0007] Component A includes cyclic olefins;

[0008] Component B includes the ruthenium carbene compound shown in formula LG;

[0009]

[0010] Among them, R1, R2, and R3 are each independently C6-C. 18 alkyl.

[0011] In one embodiment, C6-C 18 Alkyl groups are independently C6-C 10 Alkyl groups, preferably C6 alkyl, C8 alkyl, or C 10 Alkyl groups, such as C8 alkyl groups.

[0012] In one embodiment, the C6 alkyl group is independently n-hexyl or 4-methylpentyl.

[0013] In one embodiment, the C8 alkyl group is independently n-octyl, 2-ethylhexyl, or 5-methylheptyl, for example, n-octyl.

[0014] In one scheme, the C 10 The alkyl group is independently n-decane.

[0015] In a certain scheme, R1, R2, and R3 may be the same or different.

[0016] In one embodiment, the ruthenium carbene compound represented by formula LG can be any of the following compounds:

[0017]

[0018] Preferably, the ruthenium carbene compound represented by formula LG is

[0019] In one embodiment, the mass ratio of component A to component B can be (10-2500):1, preferably (600-100):1, for example 500:1 or 150:1.

[0020] In one embodiment, the cyclic olefin in component A comprises dicyclopentadiene (DCPD), and preferably, the cyclic olefin further comprises one or more of tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), and pentacyclopentadiene (PCPD).

[0021] In one embodiment, component A contains 35 wt% to 100 wt% dicyclopentadiene (DCPD), preferably, the content of dicyclopentadiene (DCPD) is 45 wt% to 95 wt%, for example 50 wt%, 55 wt%, 87 wt% or 90 wt%, where wt% is the mass percentage of each component in component A.

[0022] In one embodiment, component A contains 0 wt% to 50 wt% tricyclopentadiene (TCPD), preferably, the content of tricyclopentadiene (TCPD) is 5 wt% to 40 wt%; for example, 8 wt%, 10 wt%, 25 wt%, 26 wt%, 30 wt%, or 35 wt%, where wt% is the mass percentage of each component in component A.

[0023] In one embodiment, component A contains 0 wt% to 30 wt% tetracyclopentadiene (TeCPD), for example, 0 wt% to 20 wt%, or 0 wt%, 7.5 wt%, or 10 wt%, where wt% is the mass percentage of each component in component A.

[0024] In one embodiment, component A contains 0 wt% to 20 wt% pentacyclopentadiene (PCPD), for example, 0 wt% to 10 wt%, or 0 wt%, 2.5 wt%, 2.97 wt%, 3 wt%, or 5 wt%, where wt% is the mass percentage of each component in component A.

[0025] In one embodiment, the sum of the contents of TeCPD and PCPD in component A is 0 wt% to 35 wt%, preferably 0 wt% to 15 wt%, for example 0 wt%, 5 wt%, 15 wt%, 10 wt%, or 13 wt%.

[0026] In one embodiment, component A is any of the following:

[0027] Option a: The cyclic olefin is composed of DCPD and TCPD;

[0028] Option b: The cyclic olefin is composed of DCPD, TCPD, and TeCPD;

[0029] Scheme c: The cyclic olefin is composed of DCPD, TCPD, TeCPD and PCPD.

[0030] In one embodiment, when the cycloolefin is composed of DCPD and TCPD, the mass ratio of DCPD to TCPD can be 1:(0.05 to 0.15), for example, 90:10 or 87:8.

[0031] In one embodiment, when the cycloolefin is composed of DCPD, TCPD and TeCPD, the mass ratio of DCPD, TCPD and TeCPD can be 1:(0.2 to 0.8):(0.1 to 0.4), for example 55:35:10.

[0032] In one embodiment, when the cycloolefin is composed of DCPD, TCPD, TeCPD and PCPD, the mass ratio of DCPD, TCPD, TeCPD and PCPD can be 1:(0.3~0.8):(0.1~0.4):(0.02~0.12), for example 55:30:10:5, 50:30:10:5, 50:25:7.5:2.5 or 50:26:10:3.

[0033] In one embodiment, the cyclic olefin further comprises norbornene cyclic olefin monomers, including but not limited to one or more of norbornene, ethylidene norbornene, and tert-butyl 5-norbornene-2-carboxylate. Preferably, the norbornene cyclic olefin content in component A is 0 wt% to 10 wt%, where wt% is the mass percentage of each component in component A.

[0034] In one embodiment, component A further comprises one or more of an elastomer, a functional filler, a colorant, and a functional additive.

[0035] In one embodiment, the cyclic olefin content in component A is 60 wt% to 100 wt%, preferably 85 wt%, 89 wt%, 95 wt%, or 100 wt%, where wt% is the mass percentage of each component in component A.

[0036] In one embodiment, the content of the elastomer in component A is 0 wt% to 20 wt%, preferably 0 wt% to 10 wt%, for example 0 wt%, 2 wt%, 2.5 wt%, 3 wt% or 5 wt%, where wt% is the mass percentage of each component in component A.

[0037] In one embodiment, the content of the functional filler in component A is 0 wt% to 20 wt%, preferably 0 wt% to 15 wt%, for example 10 wt% or 5 wt%, where wt% is the mass percentage of each component in component A.

[0038] In one embodiment, the content of the color paste in component A is 0 wt% to 5 wt%, preferably 0 wt% to 3 wt%, for example 0.5 wt%, where wt% is the mass percentage of each component in component A.

[0039] In one embodiment, the content of the functional additive in component A is 0 wt% to 10 wt%, preferably 0 wt% to 5 wt%, for example 0.5 wt%, where wt% is the mass percentage of each component in component A.

[0040] In one embodiment, the elastomer in component A is a conventional elastomer in the art. Preferably, the elastomer is selected from one or more of natural rubber, isoprene rubber, ethylene propylene diene monomer (EPDM), butyl rubber, styrene-butadiene rubber, SEBS, SEPS, SBS, polyethylene (PE), and high-impact polystyrene (HIPS). For example, the elastomer is selected from one or more of SEBS, SEPS, and ethylene propylene diene monomer (EPDM).

[0041] In one embodiment, the functional filler in component A is a conventional filler in the art. Preferably, the functional filler is selected from one or more of the following: silica, graphite powder, carbon black, mica flakes, titanium dioxide, montmorillonite, carbon nanotube powder, carbon fiber powder, alumina, boehmite, hydrotalcite, basalt fiber, polyethylene fiber, glass fiber, and aramid fiber. For example, the filler is carbon black or glass fiber, preferably 800 mesh carbon black.

[0042] In one embodiment, the pigment in component A is a conventional pigment in the art, such as carbon black pigment.

[0043] In one embodiment, the functional additive in component A is a conventional additive in the art. Preferably, the functional additive is selected from one or more of polymerization regulators, antioxidants, coupling agents, and flame retardants, such as antioxidants.

[0044] In one embodiment, the polymerization regulator in component A is a conventional polymerization regulator in the art. Preferably, the polymerization regulator is selected from one or more of triphenylphosphine, triethyl phosphite, triethyl phosphate, tributyl phosphite, ethylene glycol dimethyl ether, benzophenone, and isopropyl ether.

[0045] In one embodiment, the antioxidant in component A is a conventional anti-aging agent in the art. Preferably, the antioxidant is selected from one or more of 2,6-di-tert-butyl-4-methylphenol, aniline, 2-methylaniline, BASF1010, BASF1076, BASF168, Tinuvin 571, Tinuvin 765, Tinuvin B75, Tinuvin B88, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-531, and UV-770, such as BASF168.

[0046] In one embodiment, the coupling agent in component A is a conventional coupling agent in the art, such as a silane coupling agent.

[0047] In one embodiment, the flame retardant in component A is a conventional flame retardant in the art. Preferably, the flame retardant is selected from one or more of magnesium aluminum hydrotalcite, boehmite, red phosphorus, and ammonium polyphosphate.

[0048] In one embodiment, component A is any of the following:

[0049] Scheme (1): Composed of dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD), wherein the types and contents of the dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD) are as described in any one of the present invention, and the sum of the contents of the dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD) is 100%.

[0050] Scheme (2): Composed of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and tetracyclopentadiene (TeCPD), wherein the types and contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and tetracyclopentadiene (TeCPD) are as described in any one of the present invention, and the sum of the contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and tetracyclopentadiene (TeCPD) is 100%;

[0051] Scheme (3): Composed of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD) and pentacyclopentadiene (PCPD); wherein the types and contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD) and pentacyclopentadiene (PCPD) are as described in any one of the present invention, and the sum of the contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD) and pentacyclopentadiene (PCPD) is 100%;

[0052] Scheme (4): Composed of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and an elastomer, wherein the types and contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and the elastomer are as described in any one of the present invention, and the sum of the contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD) and the elastomer is 100%;

[0053] Scheme (5): Composed of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD) and an elastomer; wherein, the types and contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD) and the elastomer are as described in any one of the present invention, and the sum of the contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD) and the elastomer is 100%;

[0054] Scheme (6): Composed of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), elastomer and functional filler; wherein, the types and contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), elastomer and functional filler are as described in any one of the present invention, and the sum of the contents of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), elastomer and functional filler is 100%;

[0055] Scheme (7): Composed of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), elastomer, color paste, and functional additives; wherein, the types and contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), elastomer, color paste, and functional additives are as described in any one of the present invention, and the sum of the contents of the dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), pentacyclopentadiene (PCPD), elastomer, color paste, and functional additives is 100%.

[0056] In one embodiment, component A is any of the following compositions:

[0057] Composition A1: 90 wt% dicyclopentadiene (DCPD) and 10 wt% tricyclopentadiene (TCPD), where wt% is the mass percentage of each component relative to component A;

[0058] Composition A2: 55 wt% dicyclopentadiene (DCPD), 35 wt% tricyclopentadiene (TCPD) and 10 wt% tetracyclopentadiene (TeCPD), where wt% is the mass percentage of each component relative to component A;

[0059] Composition A3: 55 wt% dicyclopentadiene (DCPD), 30 wt% tricyclopentadiene (TCPD), 10 wt% tetracyclopentadiene (TeCPD) and 5 wt% pentacyclopentadiene (PCPD), where wt% is the mass percentage of each component relative to component A;

[0060] Composition A4: 87 wt% dicyclopentadiene (DCPD), 8 wt% tricyclopentadiene (TCPD), 2 wt% SEBS and 3 wt% EPDM, where wt% is the mass percentage of each component relative to component A;

[0061] Composition A5: 50 wt% dicyclopentadiene (DCPD), 30 wt% tricyclopentadiene (TCPD), 10 wt% tetracyclopentadiene (TeCPD), 5 wt% pentacyclopentadiene (PCPD), 2.5 wt% SEBS and 2.5 wt% EPDM, where wt% is the mass percentage of each component relative to component A;

[0062] Composition A6: 50 wt% dicyclopentadiene (DCPD), 25 wt% tricyclopentadiene (TCPD), 7.5 wt% tetracyclopentadiene (TeCPD), 2.5 wt% pentacyclopentadiene (PCPD), 2.5 wt% SEBS, 2.5 wt% EPDM and 10 wt% carbon black, where wt% is the mass percentage of each component relative to component A;

[0063] Composition A7: 50 wt% dicyclopentadiene (DCPD), 26 wt% tricyclopentadiene (TCPD), 10 wt% tetracyclopentadiene (TeCPD), 3 wt% pentacyclopentadiene (PCPD), 2.5 wt% EPDM, 2.5 wt% SEPS, 5 wt% glass fiber, 0.5 wt% color paste and 0.5 wt% antioxidant, where wt% is the mass percentage of each component in composition A.

[0064] In one embodiment, component B is the ruthenium carbene compound shown in LG.

[0065] In one embodiment, component B may or may not contain a solvent. The solvent generally refers to a solvent used to dissolve the catalyst or polymerization monomer, and the solvent may be DCM. Preferably, it does not contain a solvent.

[0066] In one embodiment, component B contains 0 wt% to 40 wt% of solvent, for example, 0 wt% (no solvent) or 10 wt% of solvent, where wt% is the mass percentage of each component in component B.

[0067] In one embodiment, the content of the ruthenium carbene compound shown in LG in component B is 5 wt% to 100 wt%, for example, 10 wt% or 100 wt%; preferably 60 wt% to 100 wt%, where wt% is the mass percentage of each component in component B.

[0068] In one embodiment, component B further comprises an organophosphorus polymerization regulator, for example, the content of the organophosphorus polymerization regulator is 0-40 wt%, where wt% is the mass percentage of each component in component B.

[0069] In one embodiment, the organophosphorus polymerization regulator in component B is a conventional organophosphorus polymerization regulator in the art. Preferably, the organophosphorus polymerization regulator is selected from one or more of triphenylphosphine, triethyl phosphite, triethyl phosphate, and tributyl phosphite. Preferably, component B does not contain the above-mentioned organophosphorus polymerization regulator.

[0070] In one embodiment, component B may or may not contain chlorinated paraffin.

[0071] In one embodiment, component B may or may not contain an unsaturated anhydride / ester compound with a C=C structure in its molecule (for example, the unsaturated anhydride / ester compound with a C=C structure in its molecule is selected from one or more of diethyl maleate, 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, methylnadic anhydride and dimethyl 5-norbornene-2,3-dicarboxylate).

[0072] Preferably, component B does not contain the above-mentioned chlorinated paraffin and the above-mentioned unsaturated acid anhydride / ester compound containing a C=C structure in its molecule.

[0073] This invention provides an application of component B in the polymerization of catalytic component A to obtain a cyclic olefin resin, preferably, component A and component B as described in any one of the present invention.

[0074] This invention provides a method for preparing a cyclic olefin resin, which includes the following steps: mixing component A and component B, and curing them to obtain the cyclic olefin resin.

[0075] In one embodiment, the mixing conditions in the preparation method are conventional mixing conditions in the art, such as mixing in a RIM device.

[0076] In one embodiment, the curing and molding process in the preparation method can be RIM, RTM, or VARI, with RIM being the preferred method.

[0077] In the preparation method, the curing temperature of the RIM molding is a conventional curing temperature in the art, for example, a curing temperature of 40℃~100℃, or 80℃.

[0078] In the preparation method, the curing time of the RIM molding is the conventional curing time in the art, for example, the curing time is 5 minutes to 6 hours, or for example, the curing time is 3 hours.

[0079] The method for preparing the cyclic olefin resin may further include the following step of preparing component A: mixing the above-mentioned cyclic olefins to obtain component A.

[0080] Preferably, the step of preparing component A is carried out under a protective gas.

[0081] In one embodiment, in the step of preparing component A, the protective gas is a conventional protective gas in the art, preferably nitrogen.

[0082] In one embodiment, in the step of preparing component A, the mixing conditions are conventional mixing conditions in the art, such as 60°C to 80°C, stirring for 2 to 24 hours, preferably, the stirring speed is 250 rpm.

[0083] In one embodiment, the mixing conditions in the step of preparing component A are as follows:

[0084] Temperature: 60℃, stirring time: 2h, stirring speed: 250rpm;

[0085] Alternatively, temperature: 80℃, stirring time: 24h, stirring speed: 250rpm;

[0086] In one embodiment, the method for preparing the cyclic olefin resin may further include the following step of preparing component B: mixing the ruthenium carbene compound represented by the above formula LG with the above solvent to obtain component B;

[0087] Preferably, the step of preparing component B is carried out under a protective gas.

[0088] In one embodiment, during the step of preparing component B, the protective gas is a conventional protective gas in the art, preferably nitrogen.

[0089] In one embodiment, the mixing conditions in the step of preparing component B are conventional mixing conditions in the art, such as stirring for 10 minutes.

[0090] The present invention provides a cyclic olefin resin, wherein the monomers of the cyclic olefin resin include 45wt% to 95wt% of DCPD, 5wt% to 40wt% of TCPD and 2wt% to 35wt% of macrocyclic olefins, wherein the macrocyclic olefins are TeCPD and / or PCPD, and wt% is the mass percentage of each component in the monomers of the cyclic olefin resin.

[0091] Preferably, the cyclic olefin resin is obtained by mixing the above-mentioned component B and the monomer of the cyclic olefin resin, and then curing and molding it, wherein the mixing is as described in any one of the present invention, and the curing and molding is as described in any one of the present invention.

[0092] In one embodiment, the DCPD content in the monomer of the cyclic olefin resin is 50wt% to 60wt%, for example, 50wt% or 55wt%, where wt% is the mass percentage of each component relative to the monomer of the cyclic olefin resin.

[0093] In one embodiment, the content of TCPD in the monomer of the cyclic olefin resin is 20wt% to 40wt%; for example, 25wt%, 26wt%, 30wt% or 35wt%, where wt% is the mass percentage of each component in the monomer of the cyclic olefin resin.

[0094] In one embodiment, the content of TeCPD in the monomer of the cyclic olefin resin is 5 wt% to 15 wt%, for example 7.5 wt% or 10 wt%, where wt% is the mass percentage of each component relative to the monomer of the cyclic olefin resin.

[0095] In one embodiment, the content of PCPD in the monomer of the cyclic olefin resin is 0 wt% to 10 wt%, for example, 0 wt%, 2.5 wt%, 3 wt% or 5 wt%, where wt% is the mass percentage of each component in the monomer of the cyclic olefin resin.

[0096] In one embodiment, the total content of TeCPD and PCPD in the monomers of the cyclic olefin resin is 5 wt% to 35 wt%, preferably 5 wt% to 15 wt%, for example 15 wt%, 10 wt% or 13 wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin.

[0097] In one embodiment, the monomers of the cyclic olefin resin are composed of DCPD, TCPD and TeCPD. Preferably, the mass ratio of DCPD, TCPD and TeCPD can be 1:(0.2-0.8):(0.1-0.4), for example 55:35:10.

[0098] In one embodiment, when the monomers of the cyclic olefin resin are composed of DCPD, TCPD, TeCPD and PCPD, preferably, the mass ratio of DCPD, TCPD, TeCPD and PCPD can be 1:(0.3~0.8):(0.1~0.4):(0.02~0.12), for example 55:30:10:5, 50:30:10:5, 50:25:7.5:2.5 or 50:26:10:3.

[0099] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0100] The reagents and raw materials used in this invention are all commercially available.

[0101] The positive and progressive effects of the present invention are as follows: the composition provided by the present invention has good stability, the resulting polymer resin has good properties, good rigidity and strength, and the ruthenium carbene compound represented by formula LG provided by the present invention is in liquid state, has good stability, can be prepared and used immediately, and has good reactivity. Detailed Implementation

[0102] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0103] In the embodiments of this application, the tensile strength, tensile modulus and elongation at break of the obtained resin material were determined in accordance with GB / T2567.

[0104] Notched impact strength was determined according to ISO-180.

[0105] The mass loss rate of the cured material compared to the raw materials used = 1 - (mass of the obtained resin material / mass of the raw materials used);

[0106] Method for determining the average depth of surface marks: Measure the depth of all marks on the surface of the product using vernier calipers and take the average value.

[0107] Preparation Examples

[0108] Synthesis of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(trioctylphosphine)ruthenium dichloride catalyst Ru-II

[0109]

[0110] Under nitrogen protection, 50 mL of anhydrous pyridine was added to a dry 100 mL single-necked flask equipped with a magnetic stirrer, followed by 8.49 g (10.0 mmol) of ruthenium compound 1 (molecular formula: C).46 H 65 Cl2N2PRu (molecular weight: 848.97) was stirred to dissolve the catalyst solid. The reaction mixture was stirred at room temperature for 5.0 h. At this point, the solution turned dark green. Stirring was stopped, and the reaction mixture was added dropwise to a beaker containing 200 mL of petroleum ether while continuously and vigorously stirring. During this process, a green precipitate slowly precipitated from the reaction solution. After the reaction was completed, the reaction solution was filtered to obtain a green solid. The solid was washed three times with petroleum ether to remove adsorbed pyridine, and dried under vacuum to give complex 2, weighing 6.5 g (8.94 mmol), with a yield of 89.4%.

[0111] Analyze the data:

[0112] C 38 H 42 Theoretical (calculated) values ​​of Cl2N4Ru: C, 62.80 (62.62); H, 5.83 (5.60); N, 7.71 (7.61).

[0113] 1 H NMR (400MHz, CDCl3): δ19.67(s,1H,CHPh),8.84(br.s,2H,pyridine),8.39(br.s,2H,pyridine),8.07(d,2H,ortho CH,J H-H =8Hz), 7.15(t,1H,para CH,J H-H =7Hz),6.83-6.04(br.mulitiple peaks,9H,pyridine,Mes-CH),3.37(br.d,4H,CH2CH2),2.79(br.s,6H,Mes-CH3),2.45(br.s,6H,Mes-CH3),2.04(br.s,6H,Mes-CH3).

[0114] 13 C{1H}NMR(C6D6): δ314.90(m,Ru=CHPh),219.10(s,Ru-C(N)2),152.94,150.84,139.92,138.38,13 6.87,135.99,134.97,131.10,130.11,129.88,128.69,123.38,51.98,51.37,21.39,20.96,19.32

[0115] Under nitrogen protection, 3.63 g (5.00 mmol) of complex 2 was added to a dry 100 mL flask, followed by stirring in 20 mL of dichloromethane until dissolved. Then, 3.71 g (10.00 mmol) of trioctylphosphine (molecular formula: C) was added to the flask. 24 H 51 P; molecular weight: 370.65 g / mol), and the reaction mixture was stirred at room temperature for 2 h. During this process, the solution gradually changed from green to brownish-red. After the reaction was complete, the solvent was removed by rotary evaporation, and the residue was subjected to column chromatography (using a petroleum ether / dichloromethane mixture as the developing solvent) to remove the solvent, yielding a reddish-brown viscous catalyst Ru-II (molecular formula: C). 52 H 83 Cl2N2PRu (molecular weight: 939.19 g / mol) yielded 3.46 g (3.68 mmol) of a reddish-brown viscous liquid, with a yield of 73.7%.

[0116] Analyze the data:

[0117] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2PRu: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0118] 1 H NMR(400MHz, CDCl3): δ18.80(s.,1H,CHPh),7.81(d., 3 J = 6.46 Hz.2H), 7.33 (t., 3 J = 7.65 Hz, 1H), 7.04 (t., 3 J=7.80Hz,2H),6.90(s.,2H),6.24(s.,2H),4.01(m.,2H),3.85(m.,2H),2.57 (s.,6H),2.23(s.,3H),2.18(s.,6H),1.86(s.,3H),1.35-0.97(br.mulitiple peaks,48H),0.78(t.,9H).

[0119] The following ruthenium carbene compounds, represented by formula LG, were prepared using the method described above:

[0120]

[0121] Example 1 Original Formula

[0122] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0123] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0124] The obtained material has a tensile strength of 51 MPa, a tensile modulus of 1902 MPa, an elongation at break of 7.9%, and a notched impact strength (ISO-180) of 19 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.9 wt%; the average depth of surface marks was 0.13 mm (4 mm resin board).

[0125]

[0126] Example 2 adds TeCPD

[0127] Preparation of component A: Add 55 parts by mass of DCPD, 35 parts by mass of TCPD and 10 parts by mass of TeCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, seal and discharge the material, and store the product in a nitrogen-sealed raw material tank.

[0128] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0129] The obtained material has a tensile strength of 56 MPa, a tensile modulus of 2048 MPa, an elongation at break of 6.5%, and a notched impact strength of 14 kJ / m. 2 (ISO-180); The mass loss rate of the material after curing compared with the raw materials used is 0.6wt%; The average depth of surface marks is 0.11mm (4mm resin board).

[0130] Example 3: Adding macrocyclic monomers

[0131] Preparation of component A: Add 55 parts by mass of DCPD, 30 parts by mass of TCPD, 10 parts by mass of TeCPD and 5 parts by mass of PCPD to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 60°C and stir for 2 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product in a nitrogen-sealed raw material tank.

[0132] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0133] The obtained material has a tensile strength of 59 MPa, a tensile modulus of 2105 MPa, an elongation at break of 7.5%, and a notched impact strength of 11 kJ / m. 2 (ISO-180); The mass loss rate of the material after curing compared with the raw materials used is 0.5wt%; The average depth of surface marks is 0.10mm (4mm resin board).

[0134] Example 4: Adding an elastomer

[0135] Preparation of component A: Add 87 parts by mass of DCPD, 8 parts by mass of TCPD, 2 parts by mass of SEBS (Kraton G1652) and 3 parts by mass of EPDM (Keltan 8550C) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product in a nitrogen-sealed container.

[0136] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0137] The obtained material has a tensile strength of 35 MPa, a tensile modulus of 1590 MPa, an elongation at break of 19.5%, and a notched impact strength (ISO-180) of 48 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.3wt%; the average depth of surface marks was 0.08mm (4mm resin board).

[0138] Example 5: Adding elastomers and macrocyclic olefins

[0139] Preparation of component A: Add 50 parts by mass of DCPD, 30 parts by mass of TCPD, 10 parts by mass of TeCPD, 5 parts by mass of PCPD, 2.5 parts by mass of SEBS (Kraton D1102), and 2.5 parts by mass of EPDM (Keltan 8550C) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the product in a sealed container and store it under nitrogen.

[0140] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0141] The obtained material has a tensile strength of 43 MPa, a tensile modulus of 1710 MPa, an elongation at break of 16.6%, and a notched impact strength (ISO-180) of 50 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.3wt%; the average depth of surface marks was 0.08mm (4mm resin board).

[0142] Example 6: Adding filler

[0143] Preparation of component A: Add 50 parts by mass of DCPD, 25 parts by mass of TCPD, 7.5 parts by mass of TeCPD, 2.5 parts by mass of PCPD, 2.5 parts by mass of SEBS (Kraton D1102), 2.5 parts by mass of EPDM (Keltan 8550C), and 10 parts by mass of carbon black (800 mesh) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product in a nitrogen-sealed container.

[0144] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0145] The obtained material has a tensile strength of 33 MPa, a tensile modulus of 3015 MPa, and an elongation at break of 1.8%.

[0146] Example 7: Adding short glass fibers and color paste

[0147] Preparation of component A: Add 50 parts by mass of DCPD, 26 parts by mass of TCPD, 10 parts by mass of TeCPD, 3 parts by mass of PCPD, 2.5 parts by mass of SEPS 4030, 2.5 parts by mass of EPDM (Keltan 8550C), 5 parts by mass of glass fiber, 0.5 parts by mass of black pigment (BK9007-UC), and 0.5 parts by mass of antioxidant (BASF168) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product under nitrogen sealing in a raw material tank.

[0148] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0149] The obtained material has a tensile strength of 48 MPa, a tensile modulus of 4525 MPa, and an elongation at break of 4.8%.

[0150] Example 8 Storage Stability Experiment

[0151] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0152] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen) and left to stand at room temperature for 6 months. Then, the two streams of A and B are mixed at a ratio of 500:1 using a dedicated RIM device and injected into the mold. The mold temperature is 80°C and the curing time is 3 hours.

[0153] The obtained material has a tensile strength of 51 MPa, a tensile modulus of 1890 MPa, an elongation at break of 9.2%, and a notched impact strength of 19 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.8 wt%; the average depth of surface marks was 0.12 mm (4 mm resin board).

[0154] Comparison of Comparative Example 1G2 and Example 1

[0155] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0156] Preparation of component B: Under a dry nitrogen atmosphere, 10 parts by mass of Grubbs second-generation catalyst (as shown in structural formula G2) are added to a stirred tank, and then 90 parts by mass of dichloromethane are injected into the stirred tank. After stirring for 10 minutes, the material is discharged into the corresponding tank of the dedicated RIM equipment (the tank is pre-filled with nitrogen).

[0157] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen). Using a dedicated RIM device, the two streams of A and B are mixed at a ratio of 150:1 and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0158] The obtained material has a tensile strength of 51 MPa, a tensile modulus of 1880 MPa, an elongation at break of 5.9%, and a notched impact strength of 16 kJ / m. 2 The material's mass loss rate after curing was 1.4 wt% (VOCs) compared to the raw materials used; the average depth of surface marks was 0.24 mm (4 mm resin board).

[0159]

[0160] G2: Grubbs second-generation catalyst

[0161] Comparative Example 2: Ru-II in solution

[0162] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0163] Preparation of component B: Under a dry nitrogen atmosphere, add 10 parts by mass of Ru-II to the stirred tank, then inject 90 parts by mass of dichloromethane into the stirred tank, stir for 10 minutes, and then discharge the material into the corresponding tank of the dedicated RIM equipment (the tank is pre-filled with nitrogen).

[0164] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen). Using a dedicated RIM device, the two streams of A and B are mixed at a ratio of 150:1 and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0165] The obtained material has a tensile strength of 50 MPa, a tensile modulus of 1892 MPa, an elongation at break of 6.1%, and a notched impact strength of 14 kJ / m. 2The mass loss rate of the material after curing compared with the raw materials used was 1.5wt%; the average depth of surface marks was 0.24mm (4mm resin board).

[0166] Comparative Example 3: Comparison of catalyst stability

[0167] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0168] Preparation of component B: Under a dry nitrogen atmosphere, 10 parts by mass of Grubbs second-generation catalyst (as shown in structural formula G2) were added to a stirred tank, and then 90 parts by mass of dichloromethane were injected into the stirred tank. After stirring for 10 minutes, the material was discharged into the corresponding tank of the dedicated RIM equipment (the tank was pre-filled with nitrogen) and allowed to stand for 24 hours.

[0169] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen). Using a dedicated RIM device, the two streams of A and B are mixed at a ratio of 20:1 and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0170] The resulting material is gel-like.

[0171] Comparative Example 4: Performance of pure DCPD as a cyclic olefin monomer

[0172] Preparation of polycyclic olefin resin materials: Component A (DCPD) and component B (ruthenium carbene catalyst Ru-II) were respectively packaged into corresponding tanks (the tanks were pre-filled with nitrogen and pre-heated at 40°C for 12 hours). Using a dedicated RIM device, the two streams of A and B were mixed at a ratio of 500:1 and injected into the mold. The mold temperature was 80°C and the curing time was 3 hours.

[0173] The obtained material has a tensile strength of 47 MPa, a tensile modulus of 1762 MPa, an elongation at break of 7.9%, and a notched impact strength (ISO-180) of 22 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 1.2 wt%; the average depth of surface marks was 0.14 mm (4 mm resin board).

[0174] Comparative Example 5:

[0175] Preparation of component A: Add 30 parts by mass of DCPD, 40 parts by mass of TCPD, 25 parts by mass of TeCPD and 5 parts by mass of PCPD to a stirred tank. Replace the atmosphere in the tank with high-purity nitrogen, heat to 90°C, stir for 24 hours (stirring speed: 500 rpm), cool to room temperature, and discharge the material in a sealed container. Store the product in a nitrogen-sealed raw material tank.

[0176] The resulting composition of component A precipitates a large amount of solids at the bottom, making it unsuitable for continuous production of polycyclic olefin resin materials.

[0177] Comparative Example 6:

[0178] Preparation of component A: Add 60 parts by mass of DCPD, 25 parts by mass of TeCPD and 15 parts by mass of PCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 90°C, stir for 24 hours (stirring speed: 500 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed raw material tank.

[0179] A small amount of solid powder precipitated at the bottom of the composition of component A, while the upper saturated solution was a colorless and clear solution.

[0180] Comparative Example 7:

[0181]

[0182] Complex 2 was prepared according to the preparation example. Under nitrogen protection, 3.63 g (5.00 mmol) of complex 2 was added to a dry 100 mL flask, and 20 mL of dichloromethane was stirred until dissolved. Then, 0.76 g (10.00 mmol) of trimethylphosphine (Cf: C3H9P; Mw: 76.0 g / mol) was added to the flask, and the reaction mixture was stirred at room temperature for 2 h. During this process, the solution gradually changed from green to brownish-red. After the reaction was complete, the solvent was removed by rotary evaporation to obtain 2.42 g of solid particles (Cf: C31H41Cl2N2PRuMw: 644.54 g / mol).

[0183] The final product is a solid, which does not meet the requirements for a liquid state.

Claims

1. A resin composition, characterized in that, It includes component A and component B; Component A includes cyclic olefins; Component B is a ruthenium carbene compound represented by formula LG; ; Among them, R1, R2, and R3 are each independently C6-C. 18 alkyl; The mass ratio of component A to component B is (10~2500):1; In component A, the cyclic olefin comprises DCPD and TCPD, and the DCPD content is 45wt%~95wt%, where wt% is the mass percentage of each component in component A; The content of TCPD is 5 wt% to 40 wt%, where wt% is the mass percentage of each component relative to component A.

2. The resin composition according to claim 1, characterized in that, The resin composition satisfies one or more of the following conditions: (1) The C6-C 18 Alkyl groups are independently C6-C 10 alkyl; (2) The mass ratio of component A to component B is (600~100):1; (3) In component A, the cyclic olefin further comprises one or more of TeCPD and PCPD; R1, R2 and R3 mentioned in (4) are the same or different.

3. The resin composition according to claim 1, characterized in that, The resin composition satisfies one or more of the following conditions: (1) The C6-C 18 The alkyl group is independently C6 alkyl, C8 alkyl or C 10 alkyl; The mass ratio of component A to component B in (2) is 500:1 or 150:

1.

4. The resin composition according to claim 1, characterized in that, The C6-C 18 The alkyl group is independently a C8 alkyl group.

5. The resin composition according to claim 3, characterized in that, The resin composition satisfies one or more of the following conditions: (1) The C6 alkyl group is independently n-hexyl or 4-methylpentyl; (2) The C8 alkyl group is independently n-octyl, 2-ethylhexyl, or 5-methylheptyl; And (3) C 10 The alkyl group is independently n-decane.

6. The resin composition according to claim 3, characterized in that, The C8 alkyl group is independently n-octyl.

7. The resin composition according to claim 2, characterized in that, The resin composition satisfies one or more of the following conditions: (1) Component A contains 0wt%~30wt% TeCPD, where wt% is the mass percentage of each component in component A; (2) Component A contains 0wt%~20wt% PCPD, where wt% is the mass percentage of each component in component A; (3) In component A, the sum of the contents of TeCPD and PCPD is 0 wt% to 35 wt%; The ruthenium carbene compound represented by formula LG in (4) is any of the following compounds: 。 8. The resin composition according to claim 7, characterized in that, The resin composition satisfies one or more of the following conditions: (1) Component A contains 0wt% to 20wt% of TeCPD, where wt% is the mass percentage of each component in component A; (2) Component A contains 0wt%~10wt% PCPD, where wt% is the mass percentage of each component in component A; (3) In component A, the sum of the contents of TeCPD and PCPD is 0 wt% to 15 wt%; The ruthenium carbene compound represented by formula LG in (4) is .

9. The resin composition according to claim 7, characterized in that, The resin composition satisfies one or more of the following conditions: (1) The DCPD content is 50wt%, 55wt%, 87wt% or 90wt%, where wt% is the mass percentage of each component in component A; (2) The content of TCPD is 8wt%, 10wt%, 25wt%, 26wt%, 30wt% or 35wt%, where wt% is the mass percentage of each component in component A; (3) Component A contains 0 wt%, 7.5 wt%, or 10 wt% TeCPD, where wt% is the mass percentage of each component in component A; (4) Component A contains 0 wt%, 2.5 wt%, 2.97 wt%, 3 wt% or 5 wt% PCPD, where wt% is the mass percentage of each component in Component A; In component A of (5), the contents of TeCPD and PCPD are 0wt%, 5wt%, 15wt%, 10wt%, or 13wt%.

10. The resin composition according to claim 1, characterized in that, Component A can be any of the following schemes: Option a: The cyclic olefin is composed of DCPD and TCPD; Option b: The cyclic olefin is composed of DCPD, TCPD, and TeCPD; Scheme c: The cyclic olefin is composed of DCPD, TCPD, TeCPD and PCPD.

11. The resin composition according to claim 10, characterized in that, Component A can be any of the following schemes: Option a: The cyclic olefin is composed of DCPD and TCPD; the mass ratio of DCPD to TCPD is 1:(8 / 87~0.15); Option b: The cyclic olefin is composed of DCPD, TCPD, and TeCPD; the mass ratio of DCPD, TCPD, and TeCPD is 1:(0.2~0.8):(0.1~0.4). Scheme c: The cyclic olefin is composed of DCPD, TCPD, TeCPD and PCPD; the mass ratio of DCPD, TCPD, TeCPD and PCPD is 1: (0.3~0.8): (0.1~0.4): (0.02~0.12).

12. The resin composition according to claim 10, characterized in that, Component A can be any of the following schemes: Option a: The cyclic olefin is composed of DCPD and TCPD; the mass ratio of DCPD to TCPD is 90:10 or 87:8; Option b: The cyclic olefin is composed of DCPD, TCPD, and TeCPD; the mass ratio of DCPD, TCPD, and TeCPD is 55:35:10; Scheme c: The cyclic olefin is composed of DCPD, TCPD, TeCPD and PCPD; the mass ratio of DCPD, TCPD, TeCPD and PCPD is 55:30:10:5, 50:30:10:5, 50:25:7.5:2.5 or 50:26:10:

3.

13. The resin composition according to claim 2, characterized in that, The resin composition satisfies one or more of the following conditions: (1) The cyclic olefin further comprises norbornene cyclic olefins, wherein the norbornene cyclic olefins are selected from one or more of norbornene, ethylidene norbornene and 5-norbornene-2-carboxylic acid tert-butyl ester; Component A in (2) further comprises one or more of an elastomer, a functional filler, a colorant, and a functional additive.

14. The resin composition according to claim 13, characterized in that, The content of the norbornene cyclic olefins is 0wt%~10wt%, where wt% is the mass percentage of each component relative to component A.

15. The resin composition according to claim 13, characterized in that, The resin composition satisfies one or more of the following conditions: (1) In component A, the content of the cyclic olefin is 60 wt% to 100 wt%, where wt% is the mass percentage of each component in component A; (2) In component A, the content of the elastomer is 0wt%~20wt%, where wt% is the mass percentage of each component in component A; (3) In component A, the content of the functional filler is 0wt%~20wt%, where wt% is the mass percentage of each component in component A; (4) In component A, the content of the pigment is 0wt%~5wt%, where wt% is the mass percentage of each component in component A; (5) In component A, the content of the functional additive is 0wt%~10wt%, where wt% is the mass percentage of each component in component A; (6) In component A, the elastomer is selected from one or more of natural rubber, isoprene rubber, ethylene propylene rubber, ethylene propylene diene monomer (EPDM) rubber, butyl rubber, styrene-butadiene rubber, SEBS, SEPS, SBS, polyethylene, and high-impact polystyrene; (7) In component A, the functional filler is selected from one or more of the following: silica, graphite powder, carbon black, mica flakes, titanium dioxide, montmorillonite, carbon nanotube powder, carbon fiber powder, alumina, boehmite, hydrotalcite, basalt fiber, polyethylene fiber, glass fiber and aramid fiber. (8) In component A, the pigment is a carbon black pigment; In component A of (9), the functional additive is selected from one or more of polymerization regulators, antioxidants, coupling agents and flame retardants.

16. The resin composition according to claim 15, characterized in that, The resin composition satisfies one or more of the following conditions: (1) In component A, the content of the cyclic olefin is 85 wt%, 89 wt%, 95 wt% or 100 wt%, where wt% is the mass percentage of each component in component A; (2) In component A, the content of the elastomer is 0wt%~10wt%, where wt% is the mass percentage of each component in component A; (3) In component A, the content of the functional filler is 0wt%~15wt%, where wt% is the mass percentage of each component in component A; (4) In component A, the content of the pigment is 0wt%~3wt%, where wt% is the mass percentage of each component in component A; (5) In component A, the content of the functional additive is 0wt%~5wt%, where wt% is the mass percentage of each component in component A; (6) In component A, the elastomer is selected from one or more of SEBS, SEPS and EPDM rubber; (7) In component A, the functional filler is carbon black or glass fiber; In component A of (8), the functional additive is an antioxidant.

17. The resin composition according to claim 15, characterized in that, The resin composition satisfies one or more of the following conditions: (1) In component A, the content of the elastomer is 0 wt%, 2 wt%, 2.5 wt%, 3 wt% or 5 wt%, where wt% is the mass percentage of each component in component A; (2) In component A, the content of the functional filler is 10 wt% or 5 wt%, where wt% is the mass percentage of each component in component A; (3) In component A, the content of the pigment is 0.5 wt%, where wt% is the mass percentage of each component in component A; (4) In component A, the content of the functional additive is 0.5 wt%, where wt% is the mass percentage of each component in component A; In component A of (5), the functional filler is 800 mesh carbon black.

18. The resin composition according to claim 15, characterized in that, The functional adjuvant satisfies one or more of the following (a) to (d): (a) The polymerization regulator is selected from one or more of triphenylphosphine, triethyl phosphite, triethyl phosphate, tributyl phosphite, ethylene glycol dimethyl ether, benzophenone, and isopropyl ether; (b) The antioxidant is selected from one or more of 2,6-di-tert-butyl-4-methylphenol, aniline, 2-methylaniline, BASF1010, BASF1076, BASF168, Tinuvin 571, Tinuvin 765, Tinuvin B75, Tinuvin B88, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-531 and UV-770; (c) The coupling agent is a silane coupling agent; The flame retardant described in (d) is selected from one or more of magnesium aluminum hydrotalcite, boehmite, red phosphorus and ammonium polyphosphate.

19. The resin composition according to claim 18, characterized in that, The antioxidant mentioned is BASF168.

20. The resin composition according to any one of claims 1 to 19, characterized in that, Component A satisfies any of the following schemes: Scheme (1): Composed of DCPD and TCPD, wherein the content of DCPD and TCPD is as described in any one of claims 7 to 9, and the sum of the content of DCPD and TCPD is 100%; Scheme (2): Composed of DCPD, TCPD and TeCPD, wherein the content of DCPD, TCPD and TeCPD is as described in any one of claims 7 to 9, and the sum of the contents of DCPD, TCPD and TeCPD is 100%; Scheme (3): Composed of DCPD, TCPD, TeCPD and PCPD; wherein the content of DCPD, TCPD, TeCPD and PCPD is as described in any one of claims 7 to 9, and the sum of the content of DCPD, TCPD, TeCPD and PCPD is 100%; Scheme (4): Composed of DCPD, TCPD and elastomer, wherein the types and contents of DCPD, TCPD and elastomer are as described in any one of claims 7-9 or 15-17, and the sum of the contents of DCPD, TCPD and elastomer is 100%; Scheme (5): Composed of DCPD, TCPD, TeCPD, PCPD and elastomer; wherein the types and contents of DCPD, TCPD, TeCPD, PCPD and elastomer are as described in any one of claims 7-9 or 15-17, and the sum of the contents of DCPD, TCPD, TeCPD, PCPD and elastomer is 100%; Scheme (6): Composed of DCPD, TCPD, TeCPD, PCPD, elastomer and functional filler; wherein, the types and contents of DCPD, TCPD, TeCPD, PCPD, elastomer and functional filler are as described in any one of claims 7-9 or 15-19, and the sum of the contents of DCPD, TCPD, TeCPD, PCPD, elastomer and functional filler is 100%; Scheme (7): Composed of DCPD, TCPD, TeCPD, PCPD, elastomer, color paste and functional additives; wherein, the types and contents of DCPD, TCPD, TeCPD, PCPD, elastomer, color paste and functional additives are as described in any one of claims 7-9 or 15-19, and the sum of the contents of DCPD, TCPD, TeCPD, PCPD, elastomer, color paste and functional additives is 100%.

21. The resin composition according to claim 20, characterized in that, Component A satisfies any of the following schemes: Scheme (1): Component A consists of 90wt% DCPD and 10wt% TCPD, where wt% is the mass percentage of each component in Component A; Scheme (2): The component A is composed of 55wt% DCPD, 35wt% TCPD and 10wt% TeCPD, where wt% is the mass percentage of each component in the component A; Scheme (3): Component A is composed of 55wt% DCPD, 30wt% TCPD, 10wt% TeCPD and 5wt% PCPD, where wt% is the mass percentage of each component in component A; Scheme (4): Component A is composed of 87wt% DCPD, 8wt% TCPD, 2wt% SEBS and 3wt% EPDM, where wt% is the mass percentage of each component in component A; Scheme (5): Component A is composed of 50wt% DCPD, 30wt% TCPD, 10wt% TeCPD, 5wt% PCPD, 2.5wt% SEBS and 2.5wt% EPDM, where wt% is the mass percentage of each component in component A; Scheme (6): Component A is composed of 50wt% DCPD, 25wt% TCPD, 7.5wt% TeCPD, 2.5wt% PCPD, 2.5wt% SEBS, 2.5wt% EPDM and 10wt% carbon black, where wt% is the mass percentage of each component in component A; Scheme (7): Component A is composed of 50wt% DCPD, 26wt% TCPD, 10wt% TeCPD, 3wt% PCPD, 2.5wt% EPDM, 2.5wt% SEPS, 5wt% glass fiber, 0.5wt% color paste and 0.5wt% antioxidant, where wt% is the mass percentage of each component in Component A.

22. A method for preparing a cyclic olefin resin, characterized in that, It comprises the following steps: mixing component A according to any one of claims 1 to 21 and component B according to any one of claims 1 to 8, and curing to obtain a cyclic olefin resin.

23. The method for preparing the cyclic olefin resin according to claim 22, characterized in that, The preparation method satisfies one or more of the following conditions: (1) In the preparation method, the mixing condition is to mix in a RIM device; The method for preparing the cyclic olefin resin described in (2) further includes the step of preparing component A: mixing the cyclic olefins to obtain component A.

24. The method for preparing the cyclic olefin resin according to claim 22, characterized in that, The curing process is performed using RIM, RTM, or VARI methods.

25. The method for preparing the cyclic olefin resin according to claim 22, characterized in that, The curing and molding process is the RIM method.

26. The method for preparing the cyclic olefin resin according to claim 24, characterized in that, The preparation method satisfies one or more of the following conditions: (1) In the preparation method, the curing temperature of the RIM molding is 40°C. o C~100 o C; In the preparation method described in (2), the curing time of the RIM molding is 5 minutes to 6 hours.

27. The method for preparing the cyclic olefin resin according to claim 26, characterized in that, The preparation method satisfies one or more of the following conditions: (1) In the preparation method, the curing temperature of the RIM molding is 80°C. o C; In the preparation method described in (2), the curing time of the RIM molding is 3 hours.

28. The method for preparing the cyclic olefin resin according to claim 23, characterized in that, The preparation method satisfies one or more of the following conditions: (1) The step of preparing component A is carried out under a protective gas; In step (2) of preparing component A, the mixing condition is 60°C. o Stir at 80°C for 2 to 24 hours.

29. The method for preparing the cyclic olefin resin according to claim 28, characterized in that, The preparation method satisfies one or more of the following conditions: (1) The protective gas is nitrogen; The stirring speed described in (2) is 250 rpm.

30. The method for preparing the cyclic olefin resin according to claim 23, characterized in that, In the step of preparing component A, the mixing conditions are as follows: Temperature: 60℃, stirring time: 2h, stirring speed: 250rpm; Alternatively, the temperature is 80℃, the stirring time is 24h, and the stirring speed is 250rpm.

31. A cyclic olefin resin, wherein the monomers of the cyclic olefin resin comprise 45 wt% to 95 wt% DCPD, 5 wt% to 40 wt% TCPD, and 2 wt% to 35 wt% macrocyclic olefins, wherein the macrocyclic olefins are TeCPD and / or PCPD, and wt% is the mass percentage of each component in the monomers of the cyclic olefin resin; the cyclic olefin resin is obtained by mixing component B of any one of claims 1 to 8 with the monomers and then curing; the mixing conditions are as described in any one of claims 22 to 30, and the curing conditions are as described in any one of claims 22 to 30.

32. The cycloolefin resin according to claim 31, characterized in that, The monomers of the cyclic olefin resin satisfy one or more of the following conditions: (1) In the monomers of the cyclic olefin resin, the DCPD content is 50wt%~60wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin; (2) In the monomers of the cyclic olefin resin, the content of TCPD is 20 wt%~40 wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin; (3) In the monomer of the cyclic olefin resin, the content of TeCPD is 5wt%~15wt%, where wt% is the mass percentage of each component in the monomer of the cyclic olefin resin; (4) In the monomers of the cyclic olefin resin, the content of PCPD is 0wt%~10wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin; In the monomers of the cyclic olefin resin described in (5), the sum of the contents of TeCPD and PCPD is 5 wt% to 35 wt%, where wt% is the mass percentage of each component relative to the monomers of the cyclic olefin resin.

33. The cycloolefin resin according to claim 32, characterized in that, The monomers of the cyclic olefin resin satisfy one or more of the following conditions: (1) In the monomers of the cyclic olefin resin, the DCPD content is 50wt% or 55wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin. (2) In the monomers of the cyclic olefin resin, the content of TCPD is 25wt%, 26wt%, 30wt% or 35wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin. (3) In the monomers of the cyclic olefin resin, the content of TeCPD is 7.5wt% or 10wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin; (4) In the monomers of the cyclic olefin resin, the content of PCPD is 0wt%, 2.5wt%, 3wt% or 5wt%, where wt% is the mass percentage of each component in the monomers of the cyclic olefin resin; In the monomers of the cyclic olefin resin described in (5), the sum of the contents of TeCPD and PCPD is 5 wt% to 15 wt%, where wt% is the mass percentage of each component relative to the monomers of the cyclic olefin resin.

34. The cycloolefin resin according to claim 32, characterized in that, In the monomers of the cyclic olefin resin, the sum of the contents of TeCPD and PCPD is 15wt%, 10wt%, or 13wt%, where wt% is the mass percentage of each component relative to the monomers of the cyclic olefin resin.

35. The cyclic olefin resin according to claim 31, characterized in that, The monomers of the cyclic olefin resin satisfy any of the following conditions: (1) The monomers of the cyclic olefin resin are composed of DCPD, TCPD and TeCPD; When the monomers of the cyclic olefin resin described in (2) are composed of DCPD, TCPD, TeCPD and PCPD, the mass ratio of DCPD, TCPD, TeCPD and PCPD is 1:(0.3~0.8):(0.1~0.4):(0.02~0.12).

36. The cycloolefin resin according to claim 35, characterized in that, The monomers of the cyclic olefin resin are composed of DCPD, TCPD and TeCPD, and the mass ratio of DCPD, TCPD and TeCPD is 1:(0.2~0.8):(0.1~0.4).

37. The cycloolefin resin according to claim 35, characterized in that, The monomers of the cyclic olefin resin satisfy any of the following conditions: (1) The monomers of the cyclic olefin resin are composed of DCPD, TCPD and TeCPD, and the mass ratio of DCPD, TCPD and TeCPD is 55:35:10; When the monomers of the cyclic olefin resin described in (2) are composed of DCPD, TCPD, TeCPD and PCPD, the mass ratio of DCPD, TCPD, TeCPD and PCPD is 55:30:10:5, 50:30:10:5, 50:25:7.5:2.5 or 50:26:10:3.

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