Cycloolefin resin compositions, resin materials, their preparation methods and their applications

Abstract

This invention discloses a cyclic olefin resin composition, resin material, its preparation method, and its application. Specifically, this invention discloses the application of a cyclic olefin resin composition M1 in the preparation of a matrix material for high-frequency, high-speed information transmission devices. The cyclic olefin resin composition M1 comprises component A and component B, wherein component A is a cyclic olefin, and component B is a ruthenium carbene compound or its salt as shown in Formula I and / or Formula II. The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-60000). The resin material prepared using the cyclic olefin resin composition of this invention exhibits low dielectric loss (DL) under high-frequency conditions (frequency ≥ 1 GHz). f <0.001) and low dielectric constant (D k It has a strength of <2.5) and good heat resistance.

Description

Technical Field

[0001] Cycloolefin resin compositions, resin materials, their preparation methods, and their applications. Background Technology

[0002] Currently, AI and 5G high-frequency communication technologies are developing rapidly, with numerous new applications and demands emerging, leading to a continuously expanding market. Thanks to the rapid development of high-frequency, high-speed information transmission technologies, communication products are becoming increasingly faster and more multifunctional, significantly improving information processing efficiency. The development of high-frequency, high-speed information transmission technologies demands that new materials in this field possess lower dielectric constants, lower dielectric losses, and excellent heat resistance in high-frequency environments. Therefore, developing polymer materials with low dielectric constants and low dielectric losses, combined with excellent heat resistance, has become a major research focus in materials science in recent years.

[0003] Currently, a new generation of high-performance basic materials, represented by hydrocarbon resins, whose polymer structures contain only C and H elements, are rapidly developing in the field of high-frequency and high-speed information transmission. Compared with traditional materials, these materials exhibit excellent low dielectric constant (D) in high-frequency applications (frequency ≥ 1 GHz). k Low dielectric loss (D) f Properties of (D) k <3.0, D f <0.003), and the processability of such materials is much better than that of fluoropolymers (such as PTFE and PVDF).

[0004] With the development of related fields, higher requirements are now being placed on the substrate materials for next-generation high-frequency and high-speed information transmission: under high-frequency conditions (frequency ≥ 1 GHz), the dielectric loss D of the material must be... k <2.6, D f The value is less than 0.001, and considering the material's operating environment, the heat distortion temperature of the relevant material is required to be no less than 105℃. This indicator poses a significant challenge to commonly used materials.

[0005] CN113736211B and CN112646322B disclose polydicyclopentadiene / epoxy resin composites for use in the field of high-frequency copper-clad laminates. The composite material prepared by this method exhibits a dielectric constant D at 1 GHz. k >2.5, dielectric loss D f >0.01, this technical solution can no longer meet the performance requirements of the current high-frequency information transmission field.

[0006] CN111969319A discloses a method for preparing polydicyclopentadiene material using a two-component resin system, intended as a low-dielectric and low-loss material for use in 5G radio wave signal transmission equipment. However, the disclosed technical solution yields polydicyclopentadiene with a dielectric constant D at a test frequency of 1MHz. k Up to 2.78, dielectric loss D f It has reached 2.1×10 -3 The dielectric properties of the polydicyclopentadiene material prepared by this technical solution are completely inadequate to meet the material performance requirements of current high-frequency applications above 1 GHz.

[0007] CN117734286B discloses a high-temperature resistant, low-dielectric hydrocarbon resin for use in copper-clad laminates and its preparation method. The material prepared by this technical solution has a dielectric constant D. k >2.8, the performance cannot meet the requirements of high-performance, high-frequency applications.

[0008] CN117756971A discloses a method for preparing a low-dielectric hydrocarbon resin using divinylbenzene as a monomer. The polymer obtained by this method has a dielectric loss D... f The value between 0.003 and 0.0045 cannot fully meet the current needs of the high-frequency communication field.

[0009] CN111138755A states in its specification that polypropylene, as a typical low-dielectric material, has a dielectric constant D. k Between 2.0 and 2.6, the dielectric loss D f The value is 0.001 (60Hz). Since the dielectric loss of the material increases rapidly in high-frequency environments (above 1GHz), this performance index is no longer sufficient to meet the application requirements of high-performance high-frequency materials.

[0010] It is evident that the high-frequency information transmission materials reported in the existing technology have the following drawbacks:

[0011] (1) The composite obtained by combining epoxy and cyclic olefin resins has excessively high dielectric properties, especially dielectric loss under high frequency conditions.

[0012] (2) The high-frequency dielectric loss index of polydicyclopentadiene materials prepared in the traditional way is still too high;

[0013] (3) In test environments of 1 GHz and above, the dielectric properties of low dielectric hydrocarbon resin are still slightly higher than the target performance.

[0014] (4) Polypropylene materials have high high-frequency dielectric loss and low heat distortion temperature when unmodified. Summary of the Invention

[0015] The technical problem this invention aims to solve is to address the shortcomings of existing high-frequency information transmission materials, such as high dielectric constant, high dielectric loss, and poor heat resistance under high-frequency conditions, by providing a cyclic olefin resin composition and its applications. The resin material prepared using the cyclic olefin resin composition of this invention exhibits low dielectric loss (DL) under high-frequency conditions (frequency ≥ 1 GHz). f <0.001) and low dielectric constant (D k It has a strength of <2.5) and good heat resistance.

[0016] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0017] This invention provides the application of a cyclic olefin resin composition M1 in the preparation of a matrix material for high-frequency, high-speed information transmission devices. The cyclic olefin resin composition M1 comprises component A and component B, wherein component A is a cyclic olefin, and component B is a ruthenium carbene compound or its salt as shown in Formula I and / or Formula II. The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-60000).

[0018]

[0019] in,

[0020] R 11 and R 12 Each independently is C4-C 18 Alkyl or R 1-1 Replacement C4-C 18 alkyl;

[0021] R 1-1 For C6-C 10 Aryl;

[0022] R 21 R 22 and R 23 Each independently is C6-C 18 alkyl.

[0023] In one aspect of the present invention, the dielectric loss of the substrate material of the high-frequency high-speed information transmission device is <0.001 at a frequency ≥1GHz (e.g., 1-12GHz, further e.g., 10GHz), for example, dielectric loss is 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009, or 0.00091.

[0024] In one aspect of the present invention, the dielectric constant of the substrate material of the high-frequency high-speed information transmission device is <2.5 under the condition of frequency ≥1GHz (e.g., 1 to 12GHz, further e.g., 10GHz), for example, the dielectric constant is 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32.

[0025] In one embodiment of the present invention, the glass transition temperature of the substrate material of the high-frequency high-speed information transmission device is ≥135℃, for example, 138℃, 149℃, 152℃, 155℃, 157℃, 160℃, 162℃, 164℃, 165℃, 166℃, 175℃, 177℃, 186℃, 189℃ or 190℃.

[0026] In one embodiment of the present invention, the heat distortion temperature of the substrate material of the high-frequency high-speed information transmission device is ≥110℃, for example, 115℃, 117℃, 119℃, 122℃, 126℃, 127℃, 134℃, 137℃, 142℃, 144℃, 147℃, 158℃ or 167℃.

[0027] In one embodiment of the present invention, the molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-50000), for example 1:7500, 1:9500, 1:10000, 1:15000 or 1:50000.

[0028] In one embodiment of the present invention, in the cyclic olefin resin composition M1, the mass percentage of component A is 80% or more, but less than 100%.

[0029] In one embodiment of the present invention, component A is a single type of cyclic olefin or a mixture of multiple cyclic olefins, wherein the cyclic olefin contains only C and H elements, and can be produced by one or more R... A Instead, the R A Independently F, C1-C 18 Alkyl, C2-C 18 alkenyl, C6-C 10 Aryl group, carbon chain length is C2-C 18 alkoxy group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 .

[0030] In one embodiment of the present invention, component A is a single type of cyclic olefin or a mixture of multiple cyclic olefins, wherein component A contains at least cyclic olefin S1, and cyclic olefin S1 contains only C and H elements, and includes the structural segments shown below: and / or The structural fragments are connected to other parts of the molecule via carbon atoms marked with "*", and the cycloalkene S1 can be linked by one or more R... A Instead, the R A Independently F, C1-C 18 Alkyl, C2-C 18 alkenyl, C6-C 10 Aryl, C2-C 18 Alkyl group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 It can be understood that when component A is a single type of cyclic olefin, the cyclic olefin is the cyclic olefin S1.

[0031] In one embodiment of the present invention, component A is selected from tetracyclododecene, cyclopentadiene polymer, 5-ethylidene-2-norbornene, cyclohexene, cycloheptene, cyclooctene, and compounds having formula A-1. One or more of the cyclic olefins shown, in formula A, where m is 0, 1, or 2, and R A1 R A2 R A3 and R A4 Each is independently H, F, C1-C 18 Alkyl, C2-C 18 alkenyl, C6-C 10 Aryl, C2-C 18 Alkyl group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 The cyclopentadiene polymer is selected, for example, from one or more of dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, and dihydrodicyclopentadiene; the dihydrodicyclopentadiene is, for example,

[0032] In one embodiment of the present invention, component A is tetracyclododecene.

[0033] In one embodiment of the present invention, component A is dihydrodicyclopentadiene.

[0034] In one embodiment of the present invention, the component A contains 70% to 100% by mass of dicyclopentadiene, for example, 79%, 80%, 90% or 98%.

[0035] In one embodiment of the present invention, the mass percentage of tricyclopentadiene in component A is 0% to 30%, for example 10%, 15% or 20%.

[0036] In one embodiment of the present invention, component A comprises 70% to 100% dicyclopentadiene and 0% to 30% tricyclopentadiene by mass percentage.

[0037] In one embodiment of the present invention, component A is composed of the following components: 85% to 95% by mass of dicyclopentadiene and 5% to 15% by mass of tricyclopentadiene.

[0038] In one embodiment of the present invention, component A is composed of the following components: 90% to 100% by mass of dicyclopentadiene and 0% to 10% by mass of 5-ethylidene-2-norbornene.

[0039] In one embodiment of the present invention, component A is composed of the following components: 70% to 90% dicyclopentadiene, 10% to 30% tricyclopentadiene, and 0% to 5% tetracyclopentadiene by mass percentage.

[0040] In one embodiment of the present invention, component A is composed of the following components: 70% to 90% dicyclopentadiene by mass, 10% to 20% tricyclopentadiene by mass, 0% to 10% dihydrodicyclopentadiene by mass, and 0% to 5% cyclohexene by mass.

[0041] In one aspect of the present invention, component A is any one of the following:

[0042] Option 1: Component A consists of 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene;

[0043] Option 2: Component A consists of 98% by mass of dicyclopentadiene and 2% by mass of 5-ethylidene-2-norbornene;

[0044] Option 3: Component A consists of 79% by mass of dicyclopentadiene, 20% by mass of tricyclopentadiene, and 1% by mass of tetracyclopentadiene;

[0045] Option 4: Component A consists of 80% by mass of dicyclopentadiene, 15% by mass of tricyclopentadiene, 4.5% by mass of dihydrodicyclopentadiene, and 0.5% by mass of cyclohexene.

[0046] In one aspect of the present invention, in the ruthenium carbene compound as shown in Formula I, R 11 and R 12 In the context of C4-C 18 Alkyl and R 1-1 Replacement C4-C18 C4-C in alkyl groups 18 Each alkyl group is independently C4-C. 18 Straight-chain alkyl groups, such as -(CH2)3CH3, -(CH2)5CH3, -(CH2)9CH3, -(CH2) 13 CH3 or -(CH2) 17 CH3.

[0047] In one aspect of the present invention, in the ruthenium carbene compound as shown in Formula I, R 1-1 In the context of C6-C 10 The aryl group is phenyl or naphthyl, for example, phenyl.

[0048] In one aspect of the present invention, in the ruthenium carbene compound as shown in Formula I, R 11 and R 12 Each independently is C4-C 18 Alkyl groups or C4-C groups substituted with one phenyl group 18 alkyl.

[0049] In one aspect of the present invention, the ruthenium carbene compound as shown in Formula I is selected from one or more of the following compounds:

[0050]

[0051]

[0052] and / or

[0053] In one aspect of the present invention, in the ruthenium carbene compound as shown in Formula II, R 21 R 22 and R 23 In the context of C6-C 18 Each alkyl group is independently C6-C. 10 Alkyl groups, preferably C6 alkyl, C8 alkyl, or C 10 alkyl

[0054] In one aspect of the present invention, the ruthenium carbene compound as shown in Formula II is selected from one or more of the following compounds:

[0055] For example and / or

[0056] In one embodiment of the present invention, component B is a ruthenium carbene compound as shown in Formula I.

[0057] In one embodiment of the present invention, component B is a ruthenium carbene compound as shown in Formula II.

[0058] In one aspect of the present invention, component B is a ruthenium carbene compound as shown in Formula I and a ruthenium carbene compound as shown in Formula II, for example...

[0059] In one embodiment of the present invention, component B is a ruthenium carbene compound as shown in Formula I and a ruthenium carbene compound as shown in Formula II, wherein the molar ratio of the ruthenium carbene compound as shown in Formula I to the ruthenium carbene compound as shown in Formula II is 1:(1.5 to 5), for example 1:2.

[0060] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises component C, wherein component C is selected from one or more of solid paraffin, liquid paraffin, and chlorinated paraffin with a chlorine content of 5%wt to 65%wt, such as liquid paraffin, chlorinated paraffin with a chlorine content of 5%wt to 65%wt, or a mixture of liquid paraffin and chlorinated paraffin with a chlorine content of 5%wt to 65%wt, wherein the mass ratio of the liquid paraffin to the chlorinated paraffin with a chlorine content of 5%wt to 65%wt is, for example, (10 to 20):1, for example, 11:1;

[0061] Preferably, the ratio of the total mass of component C and component B to the mass of component A is 1:(15-200), for example 1:(15-55), and more preferably 1:(20-50).

[0062] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises C, wherein component C is liquid paraffin and / or chlorinated paraffin with a chlorine content of 5% wt to 65% wt, and the mass ratio of component C to component B is (15 to 70):1, for example 21:1, 28:1 or 64:1.

[0063] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises C, wherein component C is liquid paraffin, and the mass ratio of component C to component B is (60-70):1, for example 64:1.

[0064] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises C, wherein component C is chlorinated paraffin with a chlorine content of 5% wt to 65% wt, and the mass ratio of component C to component B is (15 to 35):1, for example 21:1 or 28:1.

[0065] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises component C, wherein component C is a mixture of liquid paraffin and chlorinated paraffin with a chlorine content of 5% wt to 65% wt, wherein the mass ratio of the liquid paraffin to the chlorinated paraffin with a chlorine content of 5% wt to 65% wt is, for example, (10 to 20): 1, such as 11: 1; and the mass ratio of component C to component B is (60 to 70): 1, such as 64: 1.

[0066] Preferably, in any of the above embodiments, the chlorinated paraffin with a chlorine content of 5%wt to 65%wt is a chlorinated paraffin with a chlorine content of 5%wt to 52%wt.

[0067] In one embodiment of the present invention, the cyclic olefin resin composition M1 further comprises component D, wherein component D is selected from thermoplastic resins with a carbon chain length of C. 12 The above straight-chain or branched chain olefins have a carbon chain length of C. 12 The above-mentioned linear or branched chain alkanes, solid paraffins and mineral oils include one or more of them, wherein the thermoplastic resins, chain olefins and chain alkanes contain only C and H elements.

[0068] Preferably, the thermoplastic resin is selected from one or more of ethylene propylene rubber (EP), ethylene propylene diene monomer (EPDM), thermoplastic elastomer (POE), liquid butyl rubber (LBR), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (SEBS), and styrene-butadiene-styrene block copolymer (SBS).

[0069] Preferably, the thermoplastic resin is supplemented with additives, which are organophosphorus compounds and / or antioxidants. The organophosphorus compounds are selected from one or more of triphenylphosphine, tricyclohexylphosphine, trioctylphosphine, and tributylphosphine. The antioxidants are preferably hindered phenolic antioxidants, such as one or more of antioxidants 264, 1010, and 168. Preferably, the mass percentage of the additives is 0-0.5 wt%, for example, 0-0.3 wt%, based on the total mass of components A and D.

[0070] Preferably, the carbon chain length is C 12 The above straight-chain or branched chain alkanes are n-pentadecanes;

[0071] Preferably, based on the total mass of components A and D, the mass percentage of component D is 0-20 wt%, more preferably 0-10 wt%.

[0072] In one embodiment of the present invention, the cyclic olefin resin composition M1 is composed of component A and component B from any of the above embodiments.

[0073] In one embodiment of the present invention, the cyclic olefin resin composition M1 is composed of component A, component B, and component C from any of the above embodiments.

[0074] In one embodiment of the present invention, the cyclic olefin resin composition M1 is composed of component A, component B, and component D from any of the above embodiments.

[0075] In one embodiment of the present invention, the cyclic olefin resin composition M1 is composed of component A, component B, component C, and component D from any of the above embodiments.

[0076] In one aspect of the present invention, the cyclic olefin resin composition M1 is composed of components from any of the following schemes:

[0077] Option C1: Component A and Component B,

[0078] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0079] The component B is

[0080] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0081] Option C2: Component A and Component B,

[0082] Component A is tetracyclododecene;

[0083] The component B is

[0084] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:15000.

[0085] Option C3: Component A and Component B,

[0086] Component A is dihydrodicyclopentadiene;

[0087] The component B is

[0088] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:15000.

[0089] Option C4: Components A, B, and C

[0090] Component A is composed of dicyclopentadiene and 5-ethylidene-2-norbornene, wherein the mass percentage of dicyclopentadiene in component A is 98% and the mass percentage of 5-ethylidene-2-norbornene in component A is 2%.

[0091] The component B is

[0092] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0093] Component C is liquid paraffin;

[0094] The ratio of the total mass of component C and component B to the mass of component A is 1:20;

[0095] Option C5: Components A, B, and C

[0096] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0097] The component B is

[0098] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0099] Component C is chlorinated paraffin with a chlorine content of 5%;

[0100] The ratio of the total mass of component C and component B to the mass of component A is 1:50;

[0101] Scheme C6: Components A, B, and C

[0102] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0103] The component B is

[0104] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0105] Component C is chlorinated paraffin with a chlorine content of 5%;

[0106] The ratio of the total mass of component C and component B to the mass of component A is 1:50;

[0107] Scheme C7: Component A and Component B

[0108] Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%.

[0109] The component B is

[0110] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0111] Scheme C8: Components A, B, and C

[0112] Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%.

[0113] The component B is

[0114] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0115] Component C is liquid paraffin;

[0116] The ratio of the total mass of component C and component B to the mass of component A is 1:200;

[0117] Scheme C9: Component A and Component B

[0118] Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%.

[0119] The component B is

[0120] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0121] Scheme C10: Component A and Component B

[0122] Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%.

[0123] The component B is

[0124] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:50000.

[0125] Scheme C11: Component A, Component B and Component C

[0126] Component A comprises dicyclopentadiene, tricyclopentadiene, dihydrodicyclopentadiene, and cyclohexene, wherein dicyclopentadiene accounts for 80% of the mass percentage of component A, tricyclopentadiene accounts for 15% of the mass percentage of component A, dihydrodicyclopentadiene accounts for 4.5% of the mass percentage of component A, and cyclohexene accounts for 0.5% of the mass percentage of component A.

[0127] The component B is

[0128] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:9500.

[0129] The component C is composed of liquid paraffin and chlorinated paraffin with a chlorine content of 52% wt, wherein the mass ratio of liquid paraffin to chlorinated paraffin with a chlorine content of 52% wt is 11:1.

[0130] The ratio of the total mass of component C and component B to the mass of component A is 1:20;

[0131] Scheme C12: Component A and Component B

[0132] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0133] The component B is composed of Composition, in which, The molar ratio is 1:2;

[0134] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0135] Scheme C13: Component A and Component B

[0136] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0137] The component B is

[0138] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:7500.

[0139] Scheme C14: Components A, B, and D

[0140] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0141] The component B is

[0142] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0143] Component D is a mixture of n-pentadecane, EPDM, SBS, and mineral oil;

[0144] Based on the total mass of components A and D, the mass percentage of n-pentadecane is 4-5%, and the mass percentages of EPDM, SBS and mineral oil are 2-3% independently;

[0145] Component C15: Components A, B, and D

[0146] Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%.

[0147] The component B is

[0148] The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000.

[0149] Component D is a mixture of n-pentadecane, cetene, EPDM, SEBS, POE, and mineral oil;

[0150] Based on the total mass of components A and D, the mass percentages of n-pentadecane are 2–4%, cetene is 0.3–1%, EPDM is 2–3%, SEBS is 0.3–1%, and POE is 0.5–1.2%.The mineral oil content is 2-3% by weight independently;

[0151] Component C16: Components A, B, and D

[0152] Component A: Composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%;

[0153] The component B is

[0154] Component D is a mixture of antioxidant 264, triphenylphosphine, n-pentadecane, EPDM, SEBS and POE;

[0155] Based on the total mass of components A and D, the mass percentage of antioxidant 264 is 0.1-0.2%, the mass percentage of triphenylphosphine is 0.02-0.1%, the mass percentage of n-pentadecane is 4-5%, the mass percentage of EPDM is 1-2%, the mass percentage of SEBS is 1-2%, and the mass percentage of POE is 1-2%.

[0156] In one embodiment of the present invention, the substrate material of the high-frequency high-speed information transmission device is a copper foil substrate.

[0157] The present invention also provides a cyclic olefin resin composition M1, which is the cyclic olefin resin composition M1 described in any of the above embodiments, wherein the mass percentage of component A in the cyclic olefin resin composition M1 is 80% or more but less than 100%.

[0158] The present invention also provides a cyclic olefin resin composition M2, characterized in that it is composed of component A from any of the above-described schemes and component B from any of the above-described schemes.

[0159] The present invention also provides a cyclic olefin resin composition M3, characterized in that it is composed of component A, component B, and component C from any of the above-described embodiments.

[0160] The present invention also provides a cyclic olefin resin composition M4, characterized in that it is composed of component A, component B, and component D from any of the above-described embodiments.

[0161] The present invention also provides a cyclic olefin resin composition M5, characterized in that it is composed of component A, component B, component C and component D from any of the above-described embodiments.

[0162] In this invention,

[0163] "Component A of any of the above schemes" means that the type, content or other characteristics of component A are as described in any of the above schemes, but are not limited to the type of component A as described in any of the above schemes;

[0164] "Component B of any of the above schemes" means that the type, content or other characteristics of component B are as described in any of the above schemes, but are not limited to the type of component B as described in any of the above schemes;

[0165] "Component C of any of the above schemes" means that the type, content or other characteristics of component C are as described in any of the above schemes, but are not limited to the type of component C as described in any of the above schemes.

[0166] "Component D of any of the above schemes" means that the type, content or other characteristics of component D are as described in any of the above schemes, but are not limited to the type of component D as described in any of the above schemes.

[0167] The present invention also provides a cyclic olefin resin material, characterized in that it is prepared from cyclic olefin resin compositions M1, M2, M3, M4 or M5 as described in any of the above embodiments.

[0168] In one aspect of the present invention, the dielectric loss of the cycloolefin resin material is <0.001 at a frequency ≥1GHz (e.g., 1-12GHz, further e.g., 10GHz), for example, dielectric loss is 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009, or 0.00091.

[0169] In one aspect of the present invention, the dielectric constant of the cycloolefin resin material is <2.5 at a frequency ≥1GHz (e.g., 1 to 12GHz, further e.g., 10GHz), for example, a dielectric constant of 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32.

[0170] In one embodiment of the present invention, the glass transition temperature of the cycloolefin resin material is ≥135℃, for example, 138℃, 149℃, 152℃, 155℃, 157℃, 160℃, 162℃, 164℃, 165℃, 166℃, 175℃, 177℃, 186℃, 189℃ or 190℃.

[0171] In one embodiment of the present invention, the heat distortion temperature of the cycloolefin resin material is ≥110℃, for example, 115℃, 117℃, 119℃, 122℃, 126℃, 127℃, 134℃, 137℃, 142℃, 144℃, 147℃, 158℃ or 167℃.

[0172] The cyclic olefin resin material can be prepared using conventional liquid molding processes in the art, such as reaction injection molding (RIM), resin transfer molding (RTM), and vacuum-assisted molding (VARI). In the reaction injection molding, resin transfer molding (RTM), and vacuum-assisted molding (VARI) processes, the molding temperature can be 40–145°C, preferably 40–90°C, for example, 40°C, 45°C, 60°C, 70°C, 80°C, or 140°C; the curing time can be 1–120 min, preferably 2–60 min, for example, 3.5 min, 5 min, 10 min, 20 min, 25 min, or 30 min.

[0173] The ROMP polymerization used in the cyclic olefin resin material of this invention is a front-end polymerization technology, meaning that once the reaction is initiated, it is essentially completed within a few seconds, typically with an initiation time of 15–90 seconds (adjustable). After the front-end polymerization is completed, the subsequent heat preservation process mainly aims to increase the degree of polymerization or the degree of crosslinking of the material to a certain extent. Therefore, once the initiation is completed within the range of 40–145°C, the minimum performance requirements of this invention are already met.

[0174] The present invention also provides a method for preparing a cyclic olefin resin material, characterized in that it comprises the following steps: using the cyclic olefin resin composition M1, M2, M3, M4 or M5 described in any of the above schemes as raw materials, the components in the resin composition are mixed by liquid molding process, and then cured to obtain the cyclic olefin resin material, wherein the curing temperature is 40 to 145°C and the curing time is 1 to 120 min.

[0175] In one embodiment of the present invention, the curing temperature is 40°C, 45°C, 60°C, 70°C, 80°C or 140°C.

[0176] In one aspect of the present invention, the curing time is 2 to 60 minutes, for example 3 to 30 minutes, and more specifically 3.5 minutes, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes.

[0177] In one embodiment of the present invention, the liquid molding process is reaction injection molding (RIM), resin transfer molding (RTM), or vacuum-assisted molding (VARI).

[0178] In one embodiment of the present invention, the liquid molding process is resin transfer molding (RTM) process, which includes the following steps: adding a mixture of each component in the cyclic olefin resin composition M1, M2, M3, M4 or M5 into a mold and curing it.

[0179] In one embodiment of the present invention, the liquid molding process is a reaction injection molding (RIM) process, and the raw material is the cyclic olefin resin composition M3, which includes the following steps: adding a mixture of the components of the cyclic olefin resin composition M3 into a mold and curing it.

[0180] Preferably, the mixture of the components of the cyclic olefin resin composition M3 is obtained by mixing the components of the cyclic olefin resin composition M3 at 1 to 3 MPa (e.g., 2 MPa).

[0181] Preferably, the mixture of each component of the cyclic olefin resin composition M3 is added to the mold within 4 to 6 seconds (e.g., 5 seconds).

[0182] In one embodiment of the present invention, the liquid molding process is a vacuum-assisted molding (VARI) process, which includes the following steps: adding a mixture of each component in the cyclic olefin resin composition M1, M2, M3, M4 or M5 into a mold and curing it.

[0183] In one embodiment of the present invention, in the reaction injection molding (RIM) process, resin transfer molding (RTM) process, or vacuum assisted molding (VARI) process, the mixture is a mixture of component A in each resin composition and other components in each resin composition. Component A can be treated as follows: stirred at 60°C to 125°C for 4 to 12 hours, and cooled to room temperature for later use.

[0184] In one embodiment of the present invention, in the reaction injection molding (RIM) process, resin transfer molding (RTM) process, or vacuum assisted molding (VARI) process, the temperature of the mold is 40 to 145°C.

[0185] Preferably, in the reaction injection molding (RIM) process or resin transfer molding (RTM) process, the mold temperature on one side is 40–145°C (e.g., 60–140°C), and the mold temperature on the other side is 40–145°C (e.g., 40–140°C).

[0186] More preferably, in the reaction injection molding (RIM) process or resin transfer molding (RTM) process, the temperature of the mold is any one of the following:

[0187] Option 1: One side of the mold temperature is 70℃, and the other side of the mold temperature is 40℃;

[0188] Option 2: One side of the mold temperature is 80℃, and the other side of the mold temperature is 45℃;

[0189] Option 3: One side of the mold temperature is 140℃, and the other side of the mold temperature is 140℃;

[0190] Option 4: One side of the mold temperature is 60℃, and the other side of the mold temperature is 40℃.

[0191] In one embodiment of the present invention, the reaction injection molding (RIM) process, resin transfer molding (RTM) process, or vacuum assisted molding (VARI) process further includes a post-curing stage, wherein the temperature of the post-curing process is 60–145°C (e.g., 140°C) and the post-curing time is 0–60 min (e.g., 20 min).

[0192] The present invention also provides a cyclic olefin resin material prepared by the preparation method of the cyclic olefin resin material described in any of the above embodiments.

[0193] In one aspect of the present invention, the dielectric loss of the cycloolefin resin material is <0.001 at a frequency ≥1GHz (e.g., 1-12GHz, further e.g., 10GHz), for example, dielectric loss is 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009, or 0.00091.

[0194] In one aspect of the present invention, the dielectric constant of the cycloolefin resin material is <2.5 at a frequency ≥1GHz (e.g., 1 to 12GHz, further e.g., 10GHz), for example, a dielectric constant of 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32.

[0195] In one embodiment of the present invention, the glass transition temperature of the cycloolefin resin material is ≥135℃, for example, 138℃, 149℃, 152℃, 155℃, 157℃, 160℃, 162℃, 164℃, 165℃, 166℃, 175℃, 177℃, 186℃, 189℃ or 190℃.

[0196] In one embodiment of the present invention, the heat distortion temperature of the cycloolefin resin material is ≥110℃, for example, 115℃, 117℃, 119℃, 122℃, 126℃, 127℃, 134℃, 137℃, 142℃, 144℃, 147℃, 158℃ or 167℃.

[0197] The present invention also provides a method for reducing the dielectric constant and / or dielectric loss of a cyclic olefin resin material, characterized in that it includes: when preparing the cyclic olefin resin material, introducing component B of any of the above-described schemes into component A, wherein the molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-60000).

[0198] Preferably, the raw material for the cyclic olefin resin material is any of the cyclic olefin resin compositions M1, M2, M3, M4 or M5 described in the above embodiments;

[0199] Preferably, the method for preparing the cyclic olefin resin material is as described in any of the above-described methods for preparing cyclic olefin resin materials.

[0200] In one embodiment of the present invention, the molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-50000), for example 1:7500, 1:9500, 1:10000, 1:15000 or 1:50000.

[0201] The present invention also provides a semi-cured film comprising the cyclic olefin resin material described in any of the above embodiments.

[0202] The present invention also provides a copper foil substrate comprising the prepreg film described in any of the above embodiments.

[0203] The present invention also provides a printed circuit board comprising a copper foil substrate as described in any of the above embodiments.

[0204] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0205] The reagents and raw materials used in this invention are all commercially available.

[0206] The positive and progressive effects of this invention are as follows:

[0207] (1) The cyclic olefin resin material prepared using the cyclic olefin resin composition of the present invention as a raw material exhibits significantly lower dielectric loss and dielectric constant in the high-frequency environment (1-12 GHz, for example 10 GHz) compared to cyclic olefin resin materials prepared using conventional catalysts. k <2.5, D f <0.001; and the prepared material has good heat resistance, with a heat distortion temperature (HDT) ≥110℃ and a glass transition temperature (Tg) ≥135℃;

[0208] (2) The cyclic olefin resin system disclosed in this invention can meet the requirements of various liquid molding processes (RIM, RTM, VARI), with high molding efficiency and low energy consumption. Detailed Implementation

[0209] 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.

[0210] In the following examples, the dielectric properties (including dielectric constant and dielectric loss) of the molded material were tested according to ASTM D2520.

[0211] The heat distortion temperature (HDT) was determined according to the method specified in GB / T 1634.2-2019; the Tg value was determined by dynamic thermodynamic analysis (DMA) test using a double cantilever mode, with a test temperature range of 30 to 200℃, by measuring the storage modulus of the material during the temperature program.

[0212] Example 1: Thermosetting material example (DCPD-TCPD + Type IV catalyst + RTM)

[0213] Preparation of cyclic olefin composition: 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD) were mixed. After mixing, heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0214] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium carbene catalyst (Mw = 939.19 g / mol) as shown in Formula IV;

[0215]

[0216] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1000g of cyclic olefin composition is thoroughly mixed and dissolved with 0.69g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a 1.5mm thick mold using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0217] Material performance testing: The HDT of the obtained material is 134℃, and the Tg is 162℃; under the test frequency of 10GHz, the material's Dk = 2.28 and Df = 0.00071 were measured.

[0218] Example 2.1: Thermoplastic Material Example (DMON + Type IV Catalyst + RTM)

[0219] Cyclic olefin composition: 1000g tetracyclododecene (formula V);

[0220] Liquid ruthenium catalyst: 0.39 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0221]

[0222] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1000g of cyclic olefin composition is thoroughly mixed and dissolved with 0.39g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 15000:1). The cyclic olefin resin mixture is pumped into a mold cavity with a thickness of 1.5mm using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0223] Material performance testing: The HDT of the obtained material is 142℃, and the Tg is 190℃; under the test frequency of 10GHz, the material's Dk = 2.29 and Df = 0.00075 were measured.

[0224] Example 2.2: Thermoplastic material example (dihydrodicyclopentadiene + Formula IV catalyst + RTM)

[0225] Cyclic olefin composition: 1000g dihydrodicyclopentadiene (formula VI);

[0226] Liquid ruthenium catalyst: 0.47 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0227]

[0228] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1000g of cyclic olefin composition is thoroughly mixed and dissolved with 0.47g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 15000:1). The cyclic olefin resin mixture is pumped into a mold cavity with a thickness of 1.5mm using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0229] Material performance testing: The HDT of the obtained material is 117℃ and Tg is 152℃; under the test frequency of 10GHz, the material's Dk = 2.29 and Df = 0.00077 were measured.

[0230] Example 3: RIM process molding 1 (DCPD-ENB + type VII catalyst-paraffin)

[0231] Preparation of RIM-A cycloolefin composition: 980g of dicyclopentadiene and 20g of 5-ethylidene-2-norbornene are thoroughly mixed to form a homogeneous liquid composition;

[0232] Preparation of liquid ruthenium catalyst composition RIM-B: 0.77g of ruthenium carbene catalyst (Mw: 1017.3g / mol) as shown in Formula VII is thoroughly mixed with 49.23g of liquid paraffin to form a homogeneous liquid ruthenium catalyst composition.

[0233]

[0234] High-frequency low-dielectric material molding: The RIM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. RIM-A and RIM-B liquids are mixed at a mass ratio of 20:1 and injected into the mold (monomer:Ru molar ratio 10000:1) at an injection pressure of 2.0MPa. The mold cavity with a thickness of 1.5mm is filled within 5 seconds, and the curing time is 3.5 minutes. The molded sample is then demolded.

[0235] Material performance testing: The HDT of the obtained material is 119℃, and the Tg is 155℃; under the test frequency of 10GHz, the material's Dk = 2.23 and Df = 0.00079 were measured.

[0236] Example 4.1: RIM process forming 2 (DCPD-TCPD + type IV catalyst-chlorinated paraffin)

[0237] Preparation of RIM-A cycloolefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0238] RIM-B liquid ruthenium catalyst composition: 0.69 g of liquid ruthenium carbene catalyst of Formula IV was dissolved by thorough stirring in 19.31 g of chlorinated paraffin with a chlorine content of 5%;

[0239] High-frequency low-dielectric material molding: The RIM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. RIM-A and RIM-B liquids are mixed at a mass ratio of 50:1 and injected into the mold (monomer:Ru molar ratio 10000:1) at an injection pressure of 2.0MPa. The mold cavity with a thickness of 1.5mm is filled within 5 seconds, and the curing time is 5 minutes. After curing, the molded sample is obtained by demolding.

[0240] Molding material performance test: The HDT of the obtained material is 122℃ and Tg is 157℃; under the test frequency of 10GHz, the material's Dk = 2.31 and Df = 0.00087 were measured.

[0241] Example 4.2: RIM process forming 2 (DCPD-TCPD+ type VIII catalyst-chlorinated paraffin)

[0242] Preparation of RIM-A cycloolefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0243] RIM-B liquid ruthenium catalyst composition: 0.91 g of liquid ruthenium carbene catalyst as shown in Formula VIII is thoroughly stirred and dissolved in 19.09 g of chlorinated paraffin with a chlorine content of 5%;

[0244]

[0245] High-frequency low-dielectric material molding: The RIM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. RIM-A and RIM-B liquids are mixed at a mass ratio of 50:1 and injected into the mold (monomer:Ru molar ratio 10000:1) at an injection pressure of 2.0MPa. The mold cavity with a thickness of 1.5mm is filled within 5 seconds, and the curing time is 5 minutes. After curing, the molded sample is obtained by demolding.

[0246] Molding material performance test: The HDT of the obtained material is 126℃ and Tg is 160℃; under the test frequency of 10GHz, the material's Dk = 2.30 and Df = 0.00086 were measured.

[0247] Example 5.1: VARI process for forming (DCPD-TCPD-TeCPD+ type IV catalyst)

[0248] Preparation of cyclic olefin composition: 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD), and 10g of tetracyclopentadiene (TeCPD) were mixed. After mixing, heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0249] Liquid ruthenium catalyst: 0.66 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0250] High-frequency low-dielectric material molding: Molding was performed using the VARI process. Before molding, the mold was preheated to 70°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 0.66g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump. After curing for 5 minutes, the molded sample was demolded.

[0251] Molding material performance test: The HDT of the obtained material is 147℃ and Tg is 177℃; under the test frequency of 10GHz, the material's Dk = 2.26 and Df = 0.00067 were measured.

[0252] Example 5.2: VARI process molding (DCPD-TCPD-TeCPD + type VII catalyst-liquid paraffin)

[0253] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0254] Liquid ruthenium catalyst composition: 0.71 g of ruthenium carbene catalyst of formula VII dissolved in 4.29 g of liquid paraffin;

[0255] High-frequency low-dielectric material molding: Molding is carried out using the VARI process. Before molding begins, the mold is preheated to a temperature of 70°C. 1000g of the cyclic olefin composition and 5g of the liquid ruthenium catalyst composition are thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a mold with a thickness of 1.5mm using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0256] Material performance testing: The HDT of the obtained material is 144℃ and Tg is 175℃; under the test frequency of 10GHz, the material's Dk = 2.29 and Df = 0.00072 were measured.

[0257] Example 5.3: VARI process for molding (DCPD-TCPD-TeCPD+ type IX catalyst)

[0258] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0259] Liquid ruthenium catalyst: 0.72 g of liquid ruthenium carbene catalyst as shown in Formula IX;

[0260]

[0261] High-frequency low-dielectric material molding: Molding is carried out using the VARI process. Before molding begins, the mold is preheated to a temperature of 70°C. 1000g of the cyclic olefin composition is thoroughly mixed and dissolved with 0.72g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a mold with a thickness of 1.5mm using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0262] Material performance testing: The HDT of the obtained material is 144℃, and the Tg is 175℃; under the test frequency of 10GHz, the material's Dk = 2.28 and Df = 0.00069 were measured.

[0263] Example 6: Monomer:Ru = 50000:1 (low catalyst dosage)

[0264] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0265] Liquid ruthenium catalyst: 0.132 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0266] High-frequency low-dielectric material molding: Molding was performed using the VARI process. Before molding, the mold was preheated, with one side at 80°C and the other at 45°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 0.132g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 50000:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump. After curing for 30 minutes, the molded sample was demolded.

[0267] Material performance testing: The HDT of the obtained material is 115℃, and the Tg is 138℃; under the test frequency of 10GHz, the material's Dk = 2.27 and Df = 0.00085 were measured.

[0268] Example 7: Segmented high-temperature curing (70 / 40 for 5 min + 140 for 20 min)

[0269] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0270] Liquid ruthenium catalyst: 0.66 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0271] High-frequency low-dielectric material molding: Molding was performed using the VARI process. Before molding began, the mold was preheated, with one side at 70°C and the other at 40°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 0.66g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump and cured for 5 minutes. Then, the temperature on both sides of the mold was rapidly increased to 140°C and cured for another 20 minutes. After cooling to below 80°C, the sample was demolded.

[0272] Material performance testing: The HDT of the obtained material is 158℃, and the Tg is 189℃; under the test frequency of 10GHz, the material's Dk = 2.26 and Df = 0.00073 were measured.

[0273] Example 8: Shelf life test (6 months)

[0274] Preparation of cycloolefin composition: Mix 800g of dicyclopentadiene, 150g of tricyclopentadiene, 45g of dihydrodicyclopentadiene and 5g of cyclohexene, heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0275] Preparation of liquid ruthenium catalyst composition: 0.77g of ruthenium carbene catalyst as shown in Formula VII, 45.23g of liquid paraffin and 4g of chlorinated paraffin with a chlorine content of 52% were thoroughly mixed to form a homogeneous liquid ruthenium catalyst composition.

[0276] Prepare two sets of cyclic olefin resin compositions with the same ratio according to the above preparation method, and store one set in a cool, dry place for 6 months.

[0277] Molding of freshly prepared cyclic olefin resin composition: Molding was performed using the RIM process. Before molding, the mold was preheated to 70°C on one side and 40°C on the other. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 50g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 9500:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump, cured for 10 minutes, and then demolded to obtain the sample.

[0278] Material performance testing: The HDT of the obtained material is 127℃, and the Tg is 165℃; under the test frequency of 10GHz, the material's Dk = 2.30 and Df = 0.00089 were measured.

[0279] Molding of cyclic olefin resin composition materials stored for 6 months: Molding was carried out using the RIM process. Before molding, the mold was preheated, with one side at 70°C and the other side at 40°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 50g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 9500:1). The cyclic olefin resin mixture was pumped into a mold with a thickness of 1.5mm using an injection pump, cured for 10 minutes, and then demolded to obtain the sample.

[0280] Material performance testing: The HDT of the obtained material is 127℃ and Tg is 164℃; under the test frequency of 10GHz, the material's Dk = 2.30 and Df = 0.00088 were measured.

[0281] Example 9: Initiation system of mixed ruthenium catalyst composition (Formula IV + Formula VII catalyst composition + RTM)

[0282] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0283] Liquid ruthenium catalyst composition: 0.46 g of liquid ruthenium carbene catalyst (Mw = 939.19 g / mol) shown in Formula IV and 0.25 g of ruthenium carbene catalyst (Mw: 1017.3 g / mol) shown in Formula VII were mixed evenly to obtain the liquid ruthenium catalyst composition;

[0284] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1000g of cyclic olefin composition and 0.71g of liquid ruthenium catalyst composition are thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a 1.5mm thick mold using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0285] Material performance testing: The HDT of the obtained material is 137℃ and the Tg is 166℃; under the test frequency of 10GHz, the material's Dk = 2.29 and Df = 0.00072 were measured.

[0286] Example 10: Upper limit of Ru catalyst usage (7500:1)

[0287] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0288] Liquid ruthenium catalyst: 0.91 g of liquid ruthenium carbene catalyst (Mw = 939.19 g / mol) as shown in Formula IV;

[0289] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1000g of cyclic olefin composition and 0.91g of liquid ruthenium catalyst composition are thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 7500:1). The cyclic olefin resin mixture is pumped into a 1.5mm thick mold using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0290] Material performance testing: The HDT of the obtained material is 167℃ and the Tg is 186℃; under the test frequency of 10GHz, the material's Dk = 2.30 and Df = 0.00091 were measured.

[0291] Example 11: Thermosetting material example (DCPD-TCPD-n-pentadecane + EPDM (containing 50% mineral oil)-SBS + Formula IV catalyst + RTM)

[0292] Preparation of cyclic olefin composition: 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD) were mixed. After mixing, add to the reaction vessel; disperse 50g Keltan@4890C (EPDM, containing 25g mineral oil) and 25g Kraton@D1102 (SBS) with 50g n-pentadecane, and pour into the reaction vessel; heat to 110℃ under nitrogen protection, stir for 8 hours, and cool to room temperature for later use;

[0293] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium carbene catalyst (Mw = 939.19 g / mol) as shown in Formula IV;

[0294]

[0295] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1125g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst are thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a 1.5mm thick mold using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0296] Material performance testing: The HDT of the obtained material is 124℃, and the Tg is 151℃; under the test frequency of 10GHz, the material's Dk = 2.31 and Df = 0.00079 were measured.

[0297] Example 12: Thermosetting material example (DCPD-TCPD-n-pentadecane-cetene + EPDM (containing 50% mineral oil)-POE-SEBS + Formula IV catalyst + RTM)

[0298] Preparation of cyclic olefin composition: 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD) were mixed. After mixing, add the mixture to the reactor; disperse 50g Keltan@4890C (EPDM, containing 25g mineral oil), 10g FortifyTM C1070D (POE), and 15g Kraton@G1651 (SEBS) in a 50g n-pentadecane-cetene mixture (mass ratio 85 / 15), then pour the mixture into the reactor; heat to 110℃ under nitrogen protection, stir for 8 hours, and cool to room temperature for later use;

[0299] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium carbene catalyst (Mw = 939.19 g / mol) as shown in Formula IV;

[0300]

[0301] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1125g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst are thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a 1.5mm thick mold using an injection pump. After curing for 5 minutes, the molded sample is demolded.

[0302] Material performance testing: The HDT of the obtained material is 122℃, and the Tg is 149℃; under the test frequency of 10GHz, the material's Dk = 2.30 and Df = 0.00078 were measured.

[0303] Example 13: Thermosetting Material Example (DCPD-TCPD-n-pentadecane +-POE-SEBS + antioxidant 264 + triphenylphosphine + catalyst of formula IV + RTM)

[0304] Preparation of cyclic olefin composition: 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD) were mixed. 1.5g antioxidant 264 and 0.5g triphenylphosphine (TPP) were mixed and added to the reactor; 20g Nordel™ 6565XFC (EPDM), 15g Fortify™ C1070D (POE) and 15g Kraton@G1651 (SEBS) were dispersed in 50g n-pentadecane and then poured into the reactor; under nitrogen protection, the mixture was heated to 110°C and stirred for 8 hours, then cooled to room temperature for later use.

[0305] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium carbene catalyst (Mw = 939.19 g / mol) as shown in Formula IV;

[0306]

[0307] High-frequency low-dielectric material molding: RTM process is used for molding. Before molding, the mold is preheated, with one side at 70℃ and the other side at 40℃. 1102g of cyclic olefin composition and 0.69g of liquid ruthenium catalyst are thoroughly mixed and dissolved to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a 1.5mm thick mold using an injection pump. After curing for 9 minutes, the molded sample is demolded.

[0308] Material performance testing: The HDT of the obtained material is 127℃, and the Tg is 152℃; under the test frequency of 10GHz, the material's Dk = 2.32 and Df = 0.0009 were measured.

[0309] Example 14: Preparation process of cyclic olefin resin-glass fiber cloth semi-cured sheet

[0310] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0311] Liquid ruthenium catalyst: 0.132 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0312] 1000g of the prepared cyclic olefin composition and 0.132g of liquid ruthenium catalyst were rapidly mixed in a mixing vessel for 15min, with the system temperature controlled at 2-8℃ during mixing; the uniformly mixed resin mixture was then poured into an impregnation tank.

[0313] The glass fiber cloth is passed through an impregnation tank to allow the resin to adhere to the glass fiber cloth. Then, the impregnated glass fiber cloth is quickly passed through a 100°C thermal bridge for a total residence time of 10 seconds to obtain a semi-cured cyclic olefin resin-glass fiber cloth semi-cured sheet.

[0314] Example 15: Preparation of cycloolefin resin copper clad laminate

[0315] Four cyclic olefin resin-glass fiber cloth semi-cured sheets and two 18μm copper foils from the same batch, prepared according to the method in Example 11, were stacked in the following order: one copper foil, four cyclic olefin resin-glass fiber cloth semi-cured sheets, and one copper foil. The layers were then pressed under vacuum at 140°C for 1 hour to form a copper foil substrate. The four cured cyclic olefin resin-glass fiber cloth sheets formed the insulating layer between the copper foils.

[0316] The dielectric loss Dk of the copper-clad laminate insulating layer material is 2.8, Df is 0.0025, and the glass transition temperature Tg is 152℃.

[0317] Comparative Example 1: Using G2 (G2 catalyst has extremely low solubility in cyclic olefin resins and is prone to initiating explosive polymerization)

[0318] Preparation of cyclic olefin composition: Mix 90g of dicyclopentadiene and 10g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0319]

[0320] Sample preparation: 0.064 g of Grubbs second-generation catalyst (Formula X) solid was added to the cyclic olefin composition and stirred vigorously at room temperature (800 rpm). After stirring for 1.5 min, the catalyst powder failed to dissolve, and some areas of the resin mixture underwent violent exothermic polymerization to form clumps, while the remaining parts did not react, making it impossible to obtain a sample.

[0321] Comparative Example 2: Compared with Example 1, a G2-dichloromethane solution was used.

[0322] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0323] Preparation of ruthenium catalyst solution: Weigh 0.64g of Grubbs second-generation catalyst and dissolve it in 9.36g of dichloromethane to form G2-DCM solution;

[0324] Material molding: RTM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. 10g of the prepared ruthenium catalyst solution is added dropwise to 1000g of the cyclic olefin composition (monomer:Ru molar ratio of 10000:1), and stirred thoroughly to form a homogeneous resin composition. Then, it is rapidly pumped into a mold with a cavity thickness of 1.5mm using a metering pump. After curing for 5 minutes, the sample is demolded.

[0325] Molding material performance test: The HDT of the obtained material is 126℃ and Tg is 161℃; under the test frequency of 10GHz, the Dk = 2.38 and Df = 0.00308 of the material were measured.

[0326] Comparative Example 3: Compared with Example 1, G2-toluene solution was used.

[0327] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0328] Preparation of ruthenium catalyst solution: Weigh 0.64g of Grubbs second-generation catalyst and dissolve it in 9.36g of toluene to form G2-toluene solution;

[0329] Material molding: RTM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. 10g of the prepared ruthenium catalyst solution is added dropwise to 1000g of the cyclic olefin composition (monomer:Ru molar ratio of 10000:1), and stirred thoroughly to form a homogeneous resin composition. Then, it is rapidly pumped into a mold with a cavity thickness of 1.5mm using a metering pump. After curing for 5 minutes, the sample is demolded.

[0330] Material performance testing: The HDT of the obtained material is 124℃, and the Tg is 160℃; under the test frequency of 10GHz, the material's Dk = 2.21 and Df = 0.00106 were measured.

[0331] Comparative Example 4: Compared with Example 1, a Hoveyda-toluene catalyst solution was used.

[0332] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0333] Preparation of ruthenium catalyst solution: Weigh 0.46 g of the Hoveyda catalyst solid shown in formula XI and dissolve it in 9.54 g of toluene to form G2-toluene solution;

[0334]

[0335] Material molding: RTM process is used for molding. Before molding begins, the mold is preheated, with one side at 70℃ and the other side at 40℃. 10g of the prepared ruthenium catalyst solution is added dropwise to 1000g of the cyclic olefin composition (monomer:Ru molar ratio of 10000:1), and stirred thoroughly to form a homogeneous resin composition. Then, it is rapidly pumped into a mold with a cavity thickness of 1.5mm using a metering pump. After curing for 5 minutes, the sample is demolded.

[0336] Material performance testing: The HDT of the obtained material is 113℃, and the Tg is 149℃; under the test frequency of 10GHz, the material's Dk = 2.22 and Df = 0.00114 were measured.

[0337] Comparative Example 5: Compared with Examples 5 and 6 (catalyst concentration too low, residual catalyst).

[0338] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0339] Liquid ruthenium catalyst: 0.066 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0340] High-frequency low-dielectric material molding: Molding was performed using the VARI process. Before molding, the mold was preheated, with one side at 80°C and the other at 45°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 0.066g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 80000:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump. After curing for 30 minutes, the molded sample was demolded.

[0341] Material performance testing: The obtained material has a Tg of 65℃ and a test frequency of 10GHz. The measured Dk = 2.41 and Df = 0.00589.

[0342] Comparative Example 6.1: Compared with Examples 5 and 6 (catalyst concentration too high)

[0343] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0344] Liquid ruthenium catalyst: 1.32 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0345] High-frequency low-dielectric material molding: Molding was performed using the VARI process. Before molding, the mold was preheated, with one side at 60°C and the other at 40°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 1.32g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 5000:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump. After curing for 30 minutes, the molded sample was demolded.

[0346] Material performance testing: The heat distortion temperature (HDT) of the obtained material is 120℃, and the Tg is 144℃; under the test frequency of 10GHz, the measured Dk = 2.29 and Df = 0.00109 are as follows.

[0347] Comparative Example 6.2: Compared with Examples 5, 6, and 10 (catalyst concentration too high)

[0348] Preparation of cyclic olefin composition: Mix 790g of dicyclopentadiene, 200g of tricyclopentadiene (TCPD) and 10g of tetracyclopentadiene (TeCPD), heat to 125°C under nitrogen protection, stir for 12 hours, and cool to room temperature for later use.

[0349] Liquid ruthenium catalyst: 1.02 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0350] High-frequency low-dielectric material molding: Molding was performed using the VARI process. Before molding, the mold was preheated, with one side at 60°C and the other at 40°C. 1000g of the cyclic olefin composition was thoroughly mixed and dissolved with 1.02g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 6500:1). The cyclic olefin resin mixture was pumped into a 1.5mm thick mold using an injection pump. After curing for 30 minutes, the molded sample was demolded.

[0351] Material performance testing: The heat distortion temperature (HDT) of the obtained material is 122℃, and the Tg is 151℃; under the test frequency of 10GHz, the material's Dk = 2.29 and Df = 0.00102 were measured.

[0352] Comparative Example 7: Compared with Example 1 (molding temperature was too high and the molding time was too long, resulting in thermal aging).

[0353] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0354] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0355] Material molding: RTM process is used for molding. 1000g of cyclic olefin composition is thoroughly mixed and dissolved with 0.69g of liquid ruthenium catalyst to obtain cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture is pumped into a mold with a thickness of 1.5mm using an injection pump. The temperature is rapidly raised to 160℃ on one side and 130℃ on the other side, and cured for 180min. After curing, the product is demolded after the mold temperature drops to 80℃.

[0356] Material performance testing: The HDT of the obtained material is 147℃ and Tg is 176℃; under the test frequency of 10GHz, the material's Dk = 2.32 and Df = 0.00264 were measured.

[0357] Comparative Example 8: Compared with Example 1 (molding temperature too low, defective product)

[0358] Preparation of cyclic olefin composition: Mix 900g of dicyclopentadiene and 100g of tricyclopentadiene (TCPD), heat to 60°C under nitrogen protection, stir for 4 hours, and cool to room temperature for later use.

[0359] Liquid ruthenium catalyst: 0.69 g of liquid ruthenium carbene catalyst as shown in Formula IV;

[0360] Material molding: RTM process was used for molding. Before molding, the mold was preheated to 35℃ on one side and 35℃ on the other side. 1000g of cyclic olefin composition was thoroughly mixed and dissolved with 0.69g of liquid ruthenium catalyst to obtain a cyclic olefin resin mixture (monomer:Ru molar ratio of 10000:1). The cyclic olefin resin mixture was pumped into a mold with a thickness of 1.5mm using an injection pump. After curing for 120min, the molded sample was demolded.

[0361] Material performance testing: The HDT of the obtained material is 111℃, and the Tg is 128℃; under the test frequency of 10GHz, the material's Dk = 2.39 and Df = 0.00282 were measured.

[0362] Comparison explanation:

[0363] (1) Comparison of Example 1 and Comparative Example 1 shows that the liquid ruthenium catalyst / catalyst composition disclosed in this invention has better solubility in cyclic olefin compositions compared to conventional solid catalysts; Comparison of Example 1 and Comparative Examples 2-4 shows that the liquid ruthenium catalyst composition disclosed in this invention has a significantly lower Df value (Df<0.001) compared to the material obtained by mixing and curing solutions of conventional Grubbs second-generation catalyst and Hoveyda catalyst with the disclosed cyclic olefin composition.

[0364] (2) The comparison results of Examples 5 and 6 with Comparative Examples 5 and 6 show that when the catalyst content in the cyclic olefin resin composition is too low, the Df value increases rapidly after the material is cured due to the presence of residual monomers; when the catalyst content in the cyclic olefin resin composition is too high, the Df value increases after the material is cured due to the increase in the concentration of residual metal ions, which cannot meet the relevant application requirements.

[0365] (3) The comparison between the results of Example 1 and Comparative Example 7 shows that when the cycloolefin resin composition is cured at high temperature for a long time, the heat resistance of the material is improved, but the dielectric properties, especially the Df properties, are severely lost and cannot meet the relevant application requirements.

[0366] (4) The comparison between the results of Example 1 and Comparative Example 8 shows that when the curing temperature of the cycloolefin resin composition is too low, even after a long curing time, the dielectric properties of the material still cannot meet the relevant application requirements.

[0367] (5) The materials obtained by curing a cyclic olefin or a cyclic olefin mixed with a liquid ruthenium catalyst / catalyst composition in Examples 1-13 all achieved significantly low Df values ​​(<0.001) and Dk values ​​(<2.5).

Claims

1. The application of a cyclic olefin resin composition M1 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that, The cyclic olefin resin composition M1 comprises component A and component B, wherein component A is a cyclic olefin, and component B is a ruthenium carbene compound or a salt thereof as shown in Formula I and / or Formula II, wherein the molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-60000). in, R 11 and R 12 each independently is C4-C 18 alkyl or C4-C 1-1 alkyl substituted by R 18 alkyl; R 1-1 For C6-C 10 Aryl; R 21 R 22 and R 23 Each independently is C6-C 18 alkyl.

2. The application of the cyclic olefin resin composition M1 as described in claim 1 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that, It meets one or more of the following conditions: (1) The dielectric loss of the substrate material of the high-frequency high-speed information transmission device is <0.001 under the condition of frequency ≥1GHz, for example, the dielectric loss is 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009 or 0.00091; the frequency ≥1GHz is, for example, 1 to 12GHz, and more specifically, 10GHz; (2) The dielectric constant of the substrate material of the high-frequency high-speed information transmission device is <2.5 under the condition of frequency ≥1GHz, for example, the dielectric constant is 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32; the frequency ≥1GHz is, for example, 1 to 12GHz, and more specifically, 10GHz; (3) The glass transition temperature of the substrate material of the high-frequency high-speed information transmission device is ≥135℃, for example 138℃, 149℃, 152℃, 155℃, 157℃, 160℃, 162℃, 164℃, 165℃, 166℃, 175℃, 177℃, 186℃, 189℃ or 190℃; (4) The heat distortion temperature of the substrate material of the high-frequency high-speed information transmission device is ≥110℃, for example, 115℃, 117℃, 119℃, 122℃, 126℃, 127℃, 134℃, 137℃, 142℃, 144℃, 147℃, 158℃ or 167℃. (5) In the cyclic olefin resin composition M1, the mass percentage of component A is more than 80% but less than 100%.

3. The application of the cyclic olefin resin composition M1 as described in claim 1 in the preparation of matrix materials for high-frequency and high-speed information transmission devices, characterized in that, It meets one or more of the following conditions: (1) The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500~50000), for example 1:7500, 1:9500, 1:10000, 1:15000 or 1:50000. (2) Component A is a single type of cyclic olefin or a mixture of multiple cyclic olefins, wherein the cyclic olefin contains only C and H elements, and can be produced by one or more R... A Instead, the R A Independently F, C1-C 18 Alkyl, C2-C 18 alkenyl, C6-C 10 Aryl group, carbon chain length is C2-C 18 alkoxy group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 ; Preferably, component A is a single type of cyclic olefin or a mixture of multiple cyclic olefins, and component A contains at least cyclic olefin S1, which contains only C and H elements and includes the structural fragments shown below: The structural fragments are connected to other parts of the molecule via carbon atoms marked with "*", and the cycloalkene S1 can be linked by one or more R... A Instead, the R A Independently F, C1-C 18 Alkyl, C2-C 18 alkenyl, C6-C 10 Aryl, C2-C 18 Alkoxy group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 ; More preferably, component A is selected from tetracyclododecene, cyclopentadiene polymer, 5-ethylidene-2-norbornene, cyclohexene, cycloheptene, cyclooctene, and cycloolefins having the structure shown in Formula A-1. One or more of the following, in formula A-1, m is 0, 1 or 2, R A1 R A2 R A3 and R A4 Each is independently H, F, C1-C 18 Alkyl, C2-C 18 alkenyl, C6-C 10 Aryl, C2-C 18 Alkoxy group, -C(=O)OC2-C 18 Or -OC(=O)C2-C 18 The cyclopentadiene polymer is selected, for example, from one or more of dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, and dihydrodicyclopentadiene; the dihydrodicyclopentadiene is, for example, (2) In the ruthenium carbene compound of formula I, R 11 and R 12 In the context of C4-C 18 Alkyl and R 1-1 Replacement C4-C 18 C4-C in alkyl groups 18 Each alkyl group is independently C4-C. 18 Straight-chain alkyl groups, such as -(CH2)3CH3, -(CH2)5CH3, -(CH2)9CH3, -(CH2) 13 CH3 or -(CH2) 17 CH3; (3) In the ruthenium carbene compound as shown in Formula I, R 1-1 In the context of C6-C 10 The aryl group is phenyl or naphthyl, for example, phenyl; (4) In the ruthenium carbene compound of formula II, R 21 R 22 and R 23 In the context of C6-C 18 Each alkyl group is independently C6-C. 10 Alkyl groups, preferably C6 alkyl, C8 alkyl, or C6 alkyl. 10 alkyl; Preferably, the ruthenium carbene compound as shown in Formula II is selected from one or more of the following compounds: For example 4. The application of the cyclic olefin resin composition M1 as described in claim 1 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that... It meets one or more of the following conditions: (1) Component A is any one of the following schemes: Scheme A1: Component A is tetracyclododecene; Scheme A2: Component A is dihydrodicyclopentadiene; Scheme A3: In component A, the mass percentage of dicyclopentadiene is 70% to 100%, for example 79%, 80%, 90% or 98%; Scheme A4: In component A, the mass percentage of tricyclopentadiene is 0% to 30%, for example, 10%, 15% or 20%; (2) In the ruthenium carbene compound of formula I, R 11 and R 12 Each independently is C4-C 18 Alkyl groups or C4-C groups substituted with one phenyl group 18 alkyl; Preferably, the ruthenium carbene compound as shown in Formula I is selected from one or more of the following compounds: For example 5. The application of the cyclic olefin resin composition M1 as described in claim 1 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that, It meets one or more of the following conditions: (1) Component A comprises 70% to 100% dicyclopentadiene and 0% to 30% tricyclopentadiene by mass percentage; Preferably, component A is any of the following: Scheme B1: Component A consists of the following components: 85% to 95% by mass of dicyclopentadiene and 5% to 15% by mass of tricyclopentadiene; Scheme B2: Component A consists of the following components: 90% to 100% by mass of dicyclopentadiene and 0% to 10% by mass of 5-ethylidene-2-norbornene; Scheme B3: Component A consists of the following components: 70%–90% dicyclopentadiene, 10%–30% tricyclopentadiene, and 0%–5% tetracyclopentadiene by mass. Scheme B4: Component A consists of the following components by mass percentage: 70%–90% dicyclopentadiene, 10%–20% tricyclopentadiene, 0%–10% dihydrodicyclopentadiene, and 0%–5% cyclohexene. More preferably, component A is any of the following: Option 1: Component A consists of 90% by mass of dicyclopentadiene and 10% by mass of tricyclopentadiene; Option 2: Component A consists of 98% by mass of dicyclopentadiene and 2% by mass of 5-ethylidene-2-norbornene; Option 3: Component A consists of 79% by mass of dicyclopentadiene, 20% by mass of tricyclopentadiene, and 1% by mass of tetracyclopentadiene; Option 4: Component A is composed of 80% by mass of dicyclopentadiene, 15% by mass of tricyclopentadiene, 4.5% by mass of dihydrodicyclopentadiene, and 0.5% by mass of cyclohexene. (2) The substrate material of the high-frequency high-speed information transmission device is a copper foil substrate; (3) Component B is any one of the following schemes: Scheme D1: Component B is a ruthenium carbene compound as shown in Formula I; Scheme D2: Component B is a ruthenium carbene compound as shown in Formula II; Scheme D3: Component B is a ruthenium carbene compound as shown in Formula I and a ruthenium carbene compound as shown in Formula II, for example... The molar ratio of the ruthenium carbene compound shown in Formula I to the ruthenium carbene compound shown in Formula II is, for example, 1:(1.5 to 5), and more specifically, 1:

2.

6. The application of the cyclic olefin resin composition M1 as described in claim 1 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that, The cyclic olefin resin composition M1 further comprises component C, which is selected from one or more of solid paraffin, liquid paraffin, and chlorinated paraffin with a chlorine content of 5%wt to 65%wt, such as liquid paraffin, chlorinated paraffin with a chlorine content of 5%wt to 65%wt, or a mixture of liquid paraffin and chlorinated paraffin with a chlorine content of 5%wt to 65%wt. In the mixture, the mass ratio of the liquid paraffin to the chlorinated paraffin with a chlorine content of 5%wt to 65%wt is, for example, (10 to 20):1, and more specifically, 11:

1. Preferably, the ratio of the total mass of component C and component B to the mass of component A is 1:(15-200), for example 1:(15-55), and more preferably 1:(20-50).

7. The application of the cyclic olefin resin composition M1 as described in claim 6 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that, Component C is liquid paraffin and / or chlorinated paraffin with a chlorine content of 5% wt to 65% wt, and the mass ratio of component C to component B is (15 to 70):1, for example 21:1, 28:1 or 64:

1. Preferably, component C is any of the following: Option E1: Component C is liquid paraffin, and the mass ratio of component C to component B is (60-70):1, for example, 64:1; Scheme E2: Component C is chlorinated paraffin with a chlorine content of 5% wt to 65% wt, and the mass ratio of component C to component B is (15 to 35):1, for example 21:1 or 28:1; Scheme E3: Component C is a mixture of liquid paraffin and chlorinated paraffin with a chlorine content of 5% wt to 65% wt. In the mixture, the mass ratio of the liquid paraffin to the chlorinated paraffin with a chlorine content of 5% wt to 65% wt is, for example, (10 to 20): 1, such as 11: 1; the mass ratio of component C to component B is (60 to 70): 1, such as 64:

1.

8. The application of the cyclic olefin resin composition M1 as described in claim 6 or 7 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that, The chlorinated paraffin with a chlorine content of 5%wt to 65%wt is a chlorinated paraffin with a chlorine content of 5%wt to 52%wt.

9. The application of the cyclic olefin resin composition M1 as described in claim 1 or 6 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that... The cyclic olefin resin composition M1 further comprises component D, wherein component D is selected from thermoplastic resins with a carbon chain length of C. 12 The above straight-chain or branched chain olefins have a carbon chain length of C. 12 The above-mentioned linear or branched chain alkanes, solid paraffins and mineral oils include one or more of them, wherein the thermoplastic resins, chain olefins and chain alkanes contain only C and H elements. Preferably, the thermoplastic resin is selected from one or more of ethylene propylene rubber (EP), ethylene propylene diene monomer (EPDM), thermoplastic elastomer (POE), liquid butyl rubber (LBR), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene rubber (SEBS), and styrene-butadiene-styrene block copolymer (SBS); preferably, the thermoplastic resin is supplemented with additives, the additives being organophosphorus compounds and / or antioxidants, the organophosphorus compounds being selected, for example, one or more of triphenylphosphine, tricyclohexylphosphine, trioctylphosphine, and tributylphosphine, and the antioxidants being preferably hindered phenolic antioxidants, for example, one or more of antioxidants 264, antioxidant 1010, and antioxidant 168; preferably, based on the total mass of components A and D, the mass percentage of the additives is 0-0.5 wt%, for example, 0-0.3 wt%; Preferably, the carbon chain length is C 12 The above straight-chain or branched chain alkanes are n-pentadecanes; Preferably, based on the total mass of components A and D, the mass percentage of component D is 0-20 wt%, more preferably 0-10 wt%.

10. The application of the cyclic olefin resin composition M1 as described in claim 1 in the preparation of matrix materials for high-frequency, high-speed information transmission devices, characterized in that... The cyclic olefin resin composition M1 is any one of the following: Scheme F1: The cyclic olefin resin composition M1 is composed of component A as described in any one of claims 1-5 and component B as described in any one of claims 1-5; Scheme F2: The cyclic olefin resin composition M1 is composed of component A as described in any one of claims 1-5, component B as described in any one of claims 1-5, and component C as described in any one of claims 6-8; Scheme F3: The cyclic olefin resin composition M1 is composed of component A as described in any one of claims 1-5, component B as described in any one of claims 1-5, and component D as described in claim 9; Scheme F4: The cyclic olefin resin composition M1 is composed of component A as described in any one of claims 1-5, component B as described in any one of claims 1-5, component C as described in any one of claims 6-8, and component D as described in claim 9; Preferably, the cyclic olefin resin composition M1 is composed of components from any of the following schemes: Option C1: Component A and Component B, Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Option C2: Component A and Component B, Component A is tetracyclododecene; The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:15000. Option C3: Component A and Component B, Component A is dihydrodicyclopentadiene; The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:15000. Option C4: Components A, B, and C Component A is composed of dicyclopentadiene and 5-ethylidene-2-norbornene, wherein the mass percentage of dicyclopentadiene in component A is 98% and the mass percentage of 5-ethylidene-2-norbornene in component A is 2%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Component C is liquid paraffin; The ratio of the total mass of component C and component B to the mass of component A is 1:20; Option C5: Components A, B, and C Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Component C is chlorinated paraffin with a chlorine content of 5%; The ratio of the total mass of component C and component B to the mass of component A is 1:50; Scheme C6: Components A, B, and C Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Component C is chlorinated paraffin with a chlorine content of 5%; The ratio of the total mass of component C and component B to the mass of component A is 1:50; Scheme C7: Component A and Component B Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Scheme C8: Components A, B, and C Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Component C is liquid paraffin; The ratio of the total mass of component C and component B to the mass of component A is 1:200; Scheme C9: Component A and Component B Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Scheme C10: Component A and Component B Component A is composed of dicyclopentadiene, tricyclopentadiene and tetracyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 79%, the mass percentage of tricyclopentadiene in component A is 20%, and the mass percentage of tetracyclopentadiene in component A is 1%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:50000. Scheme C11: Component A, Component B and Component C Component A comprises dicyclopentadiene, tricyclopentadiene, dihydrodicyclopentadiene, and cyclohexene, wherein dicyclopentadiene accounts for 80% of the mass percentage of component A, tricyclopentadiene accounts for 15% of the mass percentage of component A, dihydrodicyclopentadiene accounts for 4.5% of the mass percentage of component A, and cyclohexene accounts for 0.5% of the mass percentage of component A. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:9500. The component C is composed of liquid paraffin and chlorinated paraffin with a chlorine content of 52% wt, wherein the mass ratio of liquid paraffin to chlorinated paraffin with a chlorine content of 52% wt is 11:

1. The ratio of the total mass of component C and component B to the mass of component A is 1:20; Scheme C12: Component A and Component B Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is composed of Composition, in which, The molar ratio is 1:2; The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Scheme C13: Component A and Component B Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:7500. Scheme C14: Components A, B, and D Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Component D is a mixture of n-pentadecane, EPDM, SBS, and mineral oil; Based on the total mass of components A and D, in component D, the mass percentage of n-pentadecane is 4-5%, and the mass percentages of EPDM, SBS and mineral oil are independently 2-3%. Component C15: Components A, B, and D Component A is composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%. The component B is The molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:10000. Component D is a mixture of n-pentadecane, cetene, EPDM, SEBS, POE, and mineral oil; Based on the total mass of components A and D, the mass percentage of n-pentadecane is 2-4%, the mass percentage of cetene is 0.3-1%, the mass percentage of EPDM is 2-3%, the mass percentage of SEBS is 0.3-1%, the mass percentage of POE is 0.5-1.2%, and the mass percentage of mineral oil is independently 2-3%. Component C16: Components A, B, and D Component A: Composed of dicyclopentadiene and tricyclopentadiene, wherein the mass percentage of dicyclopentadiene in component A is 90% and the mass percentage of tricyclopentadiene in component A is 10%; The component B is Component D is a mixture of antioxidant 264, triphenylphosphine, n-pentadecane, EPDM, SEBS and POE; Based on the total mass of components A and D, the mass percentage of antioxidant 264 is 0.1-0.2%, the mass percentage of triphenylphosphine is 0.02-0.1%, the mass percentage of n-pentadecane is 4-5%, the mass percentage of EPDM is 1-2%, the mass percentage of SEBS is 1-2%, and the mass percentage of POE is 1-2%.

11. A cyclic olefin resin composition M1, which is the cyclic olefin resin composition M1 as described in any one of claims 1-10, wherein the mass percentage of component A in the cyclic olefin resin composition M1 is 80% or more but less than 100%.

12. A cyclic olefin resin composition, characterized in that, It is one of the following cyclic olefin resin compositions: M2, M3, M4, or M5: Cycloolefin resin composition M2: It is composed of component A as described in any one of claims 1-5 and component B as described in any one of claims 1-5; Cycloolefin resin composition M3: It is composed of component A as described in any one of claims 1-5, component B as described in any one of claims 1-5, and component C as described in any one of claims 6-8; Cycloolefin resin composition M4: It is composed of component A as described in any one of claims 1-5, component B as described in any one of claims 1-5, and component D as described in claim 9; Cycloolefin resin composition M5: It is composed of component A as described in any one of claims 1-5, component B as described in any one of claims 1-5, component C as described in any one of claims 6-8, and component D as described in claim 9.

13. A cyclic olefin resin material, characterized in that, It is prepared using the cyclic olefin resin composition M1 as described in claim 11, the cyclic olefin resin composition M2 as described in claim 12, the cyclic olefin resin composition M3, the cyclic olefin resin composition M4, or the cyclic olefin resin composition M5 as raw materials; Preferably, the cycloolefin resin material satisfies one or more of the following conditions: (1) The dielectric loss of the cyclic olefin resin material at a frequency ≥ 1 GHz is < 0.001, for example, the dielectric loss is 0.00067, 0.00069, 0.00071, 0.00072, 0.00073, 0.00075, 0.00077, 0.00078, 0.00079, 0.00085, 0.00086, 0.00087, 0.00088, 0.00089, 0.0009 or 0.00091; the frequency ≥ 1 GHz is, for example, 1 to 12 GHz, and more specifically, 10 GHz; (2) The dielectric constant of the cyclic olefin resin material is <2.5 at a frequency ≥1GHz, for example, the dielectric constant is 2.23, 2.26, 2.27, 2.28, 2.29, 2.30, 2.31 or 2.32; the frequency ≥1GHz is, for example, 1 to 12GHz, and more specifically, 10GHz; (3) The glass transition temperature of the cycloolefin resin material is ≥135℃, for example 138℃, 149℃, 152℃, 155℃, 157℃, 160℃, 162℃, 164℃, 165℃, 166℃, 175℃, 177℃, 186℃, 189℃ or 190℃; (4) The heat distortion temperature of the cycloolefin resin material is ≥110℃, for example 115℃, 117℃, 119℃, 122℃, 126℃, 127℃, 134℃, 137℃, 142℃, 144℃, 147℃, 158℃ or 167℃. (5) The cyclic olefin resin material is prepared by liquid molding process, such as reaction injection molding, resin transfer molding and vacuum-assisted molding. In the reaction injection molding, resin transfer molding and vacuum-assisted molding processes, the molding temperature can be 40 to 145°C, preferably 40 to 90°C, such as 40°C, 45°C, 60°C, 70°C, 80°C or 140°C; the curing time can be 1 to 120 min, preferably 2 to 60 min, such as 3.5 min, 5 min, 10 min, 20 min, 25 min or 30 min.

14. A method for preparing a cyclic olefin resin material, characterized in that, It comprises the following steps: using the cyclic olefin resin composition M1 as described in claim 11, the cyclic olefin resin composition M2 as described in claim 12, the cyclic olefin resin composition M3, the cyclic olefin resin composition M4, or the cyclic olefin resin composition M5 as raw materials, the components in the resin composition are mixed through a liquid molding process, and then cured to obtain the cyclic olefin resin material, wherein the curing temperature is 40-145°C, and the curing time is 1-120 min; Preferably, the curing temperature is 40°C, 45°C, 60°C, 70°C, 80°C or 140°C; Preferably, the curing time is 2 to 60 minutes, for example 3 to 30 minutes, and more specifically 3.5 minutes, 5 minutes, 10 minutes, 20 minutes, 25 minutes, or 30 minutes. Preferably, the liquid molding process is a reaction injection molding process, a resin transfer molding process, or a vacuum-assisted molding process.

15. The method for preparing the cyclic olefin resin material as described in claim 14, characterized in that, It satisfies any one of the following conditions: (1) The liquid molding process is a resin transfer molding process, which includes the following steps: adding the mixture of each component in the cyclic olefin resin composition M1, M2, M3, M4 or M5 into the mold and curing it. (2) The liquid molding process is a reaction injection molding process, and the raw material is the cyclic olefin resin composition M3, which includes the following steps: adding the mixture of each component of the cyclic olefin resin composition M3 into the mold and curing it. Preferably, the mixture of the components of the cyclic olefin resin composition M3 is obtained by mixing the components of the cyclic olefin resin composition M3 at 1 to 3 MPa, for example 2 MPa. Preferably, the mixture of each component of the cyclic olefin resin composition M3 is added to the mold within 4 to 6 seconds, for example, 5 seconds. (3) The liquid molding process is a vacuum-assisted molding process, which includes the following steps: adding the mixture of each component in the cyclic olefin resin composition M1, M2, M3, M4 or M5 into the mold and curing it.

16. The method for preparing the cyclic olefin resin material as described in claim 15, characterized in that, It meets one or more of the following conditions: (1) In the reaction injection molding process, resin transfer molding process or vacuum-assisted molding process, the mixture is a mixture of component A in each resin composition and other components in each resin composition. Component A can be treated as follows: stirred at 60℃~125℃ for 4~12h, and cooled to room temperature for later use. (2) In the reaction injection molding process, resin transfer molding process or vacuum-assisted molding process, the temperature of the mold is 40 to 145°C. Preferably, in the reaction injection molding process or resin transfer molding process, the mold temperature on one side is 40-145°C, for example 60-140°C; and the mold temperature on the other side is 40-145°C, for example 40-140°C. More preferably, in the reaction injection molding (RIM) process or resin transfer molding (RTM) process, the temperature of the mold is any one of the following: Option 1: One side of the mold temperature is 70℃, and the other side of the mold temperature is 40℃; Option 2: One side of the mold temperature is 80℃, and the other side of the mold temperature is 45℃; Option 3: One side of the mold temperature is 140℃, and the other side of the mold temperature is 140℃; Option 4: One side of the mold temperature is 60℃, and the other side of the mold temperature is 40℃; (3) The reaction injection molding process, resin transfer molding process or vacuum-assisted molding process further includes a post-curing stage, wherein the temperature of the post-curing process is 60 to 145°C, for example 140°C, and the post-curing time is 0 to 60 min, for example 20 min.

17. A method for reducing the dielectric constant and / or dielectric loss of cyclic olefin resin materials, characterized in that, It includes: when preparing the cyclic olefin resin material, introducing component B as described in any one of claims 1-5 into component A as described in any one of claims 1-5, wherein the molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-60000). Preferably, the raw material for the cyclic olefin resin material is the cyclic olefin resin composition M1 as described in claim 11 or the cyclic olefin resin composition M2, M3, M4 or M5 as described in claim 12; Preferably, the method for preparing the cyclic olefin resin material is as described in any one of claims 14-16; Preferably, the molar ratio of Ru in component B to the monomer of the cyclic olefin in component A is 1:(7500-50000), for example 1:7500, 1:9500, 1:10000, 1:15000 or 1:50000.

18. A semi-cured film comprising the cycloolefin resin material of claim 13.

19. A copper foil substrate comprising the prepreg as described in claim 18.

20. A printed circuit board comprising a copper foil substrate as described in claim 19.

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