Inorganic enhanced polydicyclopentadiene material as well as preparation method and application thereof

Abstract

The invention provides an inorganic enhanced polydicyclopentadiene material as well as a preparation method and application thereof, and the inorganic enhanced polydicyclopentadiene material is prepared from the following raw materials in parts by weight: 70-99.5 parts of dicyclopentadiene; 0.01 to 20 parts of a surface modified inorganic filler; 0.01 to 10 parts of polymer resin; and 0.005 to 0.2 part of a catalyst. According to the invention, the preparation raw materials of the polydicyclopentadiene material simultaneously comprise the surface modified inorganic filler and the polymer resin, and the surface modified inorganic filler and the polymer resin have a synergistic effect, so that the problem that the inorganic filler is easy to settle and layer in a dicyclopentadiene material liquid is effectively solved, and the problem that the surface compatibility of the inorganic filler and the polydicyclopentadiene material is poor is solved; meanwhile, the adverse effect on the performance of the polydicyclopentadiene material caused by the use of a surface coupling agent can also be avoided. The inorganic filler reinforced dicyclopentadiene feed liquid prepared by the invention can meet the requirements of a reaction injection molding process.

Description

Technical Field

[0001] The invention belongs to the technical field of polydicyclopentadiene materials, and relates to an inorganic enhanced polydicyclopentadiene material and a preparation method and application thereof, and relates to an inorganic enhanced polydicyclopentadiene material with adjustable mechanical properties and a preparation method and application thereof. Background Art

[0002] Polydicyclopentadiene (PDCPD) is a thermosetting engineering plastic with excellent comprehensive performance, excellent mechanical properties, chemical corrosion resistance and excellent dimensional stability. The manufacturing process is a reaction injection molding process, which is simple and efficient. It is a high-quality engineering plastic that is easy to industrialize. However, for specific application fields, such as rail transportation, agricultural machinery, transportation, etc., the performance of the polydicyclopentadiene material itself is insufficient, and it is necessary to use reinforcing materials to increase its mechanical properties.

[0003] In order to solve the above-mentioned mechanical properties do not meet the actual use demand, the prior art uses inorganic fillers as reinforcing materials, and the inorganic fillers used include white carbon black, calcium carbonate, aluminum hydroxide, silicon dioxide, etc. In the prior art, inorganic reinforcing materials adopt the mode of physical blending as the main, therefore, there are problems such as poor dispersibility and poor compatibility, and the modification effect is unsatisfactory. Due to the large density of inorganic fillers, it is easy to settle and layer in the feed liquid of dicyclopentadiene material, and with the poor surface compatibility of polydicyclopentadiene (PDCPD) material, this also has a strong impact on the dispersibility and stability of inorganic fillers in dicyclopentadiene material feed liquid. Meanwhile, it is impossible to realize the mechanical property regulation of inorganic reinforced polydicyclopentadiene.

[0004] In the prior art solution, surface coupling agent is used to carry out surface modification to inorganic filler, to improve the compatibility of inorganic filler and polydicyclopentadiene (PDCPD) material, so as to improve the dispersibility and stability of inorganic filler in polydicyclopentadiene (PDCPD) material. As CN117866386A discloses a kind of nano-TiO2 modified polydicyclopentadiene resin and its preparation method and application, it uses silane coupling agent modified TiO2, the bending modulus of resin is improved to 2131-2980MPa, and tensile modulus is improved to 1938-2340MPa. In the prior art solution, although coupling agent is used to solve the dispersibility problem of inorganic filler to a certain extent, for inorganic filler with larger particle size and large density, the effect is not good, and there are still sedimentation and stratification phenomenon. At this point, not only the effective utilization rate of inorganic filler in PDCPD material is seriously affected, but also the mechanical property of inorganic reinforcing material polydicyclopentadiene material is not adjustable. At the same time, due to the failure to effectively solve the sedimentation and stratification problems, the dicyclopentadiene liquid using inorganic fillers cannot meet the requirements of the reaction injection molding process.

[0005] Therefore, in the art, it is desired to develop a polydicyclopentadiene material, in which the liquid does not have the problems of sedimentation and stratification during the preparation process, is suitable for injection molding, and has excellent mechanical properties. Summary of the invention

[0006] In view of the deficiencies of the prior art, the purpose of the present invention is to provide an inorganic reinforced polydicyclopentadiene material and a preparation method and application thereof, specifically an inorganic reinforced polydicyclopentadiene material with adjustable mechanical properties and a preparation method and application thereof. The present invention mainly solves the following problems: 1) the problem that inorganic fillers are easy to settle and stratify in dicyclopentadiene liquid; 2) the problem that inorganic fillers have poor surface compatibility with polydicyclopentadiene materials; 3) the problem that inorganic fillers cannot adjust the mechanical properties of polydicyclopentadiene; 4) the problem that dicyclopentadiene liquid containing inorganic fillers cannot use the reaction injection molding process.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an inorganic enhanced polydicyclopentadiene material, wherein the raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

[0009]

[0010]

[0011] In the present invention, the raw materials for preparing the polydicyclopentadiene material include both surface-modified inorganic fillers and polymer resins, which work synergistically to effectively solve the problem of easy sedimentation and stratification of the inorganic filler in the dicyclopentadiene liquid, and the problem of poor surface compatibility between the inorganic filler and the polydicyclopentadiene material, and at the same time, the adverse effect of using a surface coupling agent on the performance of the polydicyclopentadiene material can be avoided. The inorganic filler-reinforced dicyclopentadiene liquid prepared by the present invention can meet the requirements of the reaction injection molding process.

[0012] In the present invention, the polymer resin is used as a viscosity regulator, and can be appropriately adjusted according to the particle size and density of the inorganic filler, so that the inorganic fillers with different particle sizes and densities can be effectively dispersed in the dicyclopentadiene solution.

[0013] In the present invention, the raw materials for preparing the inorganic enhanced polydicyclopentadiene material are calculated by weight, and the amount of dicyclopentadiene used can be 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 99 parts, 99.5 parts, etc.

[0014] In the present invention, the raw materials for preparing the inorganic reinforced polydicyclopentadiene material are measured by weight, and the amount of the surface modified inorganic filler can be 0.01 parts, 0.02 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.

[0015] In the present invention, the raw materials for preparing the inorganic enhanced polydicyclopentadiene material are measured in parts by weight, and the amount of the polymer resin can be 0.01 parts, 0.02 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.

[0016] In the present invention, the raw materials for preparing the inorganic enhanced polydicyclopentadiene material are measured by weight, and the amount of the catalyst used can be 0.005 parts, 0.006 parts, 0.008 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.16 parts, 0.18 parts, 0.2 parts, etc.

[0017] Preferably, the surface-modified inorganic filler includes an inorganic filler whose surface is modified by a silane coupling agent.

[0018] Preferably, the silane coupling agent includes any one of alkyl silane coupling agent, vinyl silane coupling agent, epoxy silane coupling agent, silane polymer, amino silane, phenyl silane or a combination of at least two thereof. The alkane chain, vinyl group, epoxy group and the like in the silane coupling agent can not only increase the dispersibility of the inorganic filler, but also enhance the interface performance between the inorganic filler and the polydicyclopentadiene material.

[0019] Preferably, the vinyl silane coupling agent includes any one of vinyl triethoxy silane (A151), vinyl tri (2-methoxyethoxy) silane (A171), vinyl tri (2-methoxyethoxy) silane (A172), vinyl triisopropoxy silane (KH1706), and methyl vinyl dimethoxy silane (KH1710), or a combination of at least two thereof.

[0020] Preferably, the epoxy silane coupling agent includes any one of γ-glycidyloxypropyltrimethoxysilane (KH560), 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane (KH781), γ-glycidyloxypropyltriethoxysilane (KH561), γ-glycidyloxypropyltriethoxysilane (KH1770), and 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane (KH78), or a combination of at least two thereof.

[0021] Preferably, the inorganic filler includes any one of white carbon black, calcium carbonate, aluminum hydroxide, silicon dioxide, carbon black, or a combination of at least two thereof. The inorganic filler used in the present invention has high hardness, high heat resistance and good chemical stability.

[0022] Preferably, the particle size of the inorganic filler is 1 to 100 nm, for example, 1 nm, 3 nm, 5 nm, 8 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, etc.

[0023] Preferably, the surface modified inorganic filler is prepared by the following method:

[0024] The inorganic filler is mixed with an alcohol solvent, heated, then a silane coupling agent is added, reacted, the alcohol solvent is removed, and dried to obtain the surface-modified inorganic filler.

[0025] Preferably, the alcohol solvent includes any one of methanol, ethanol, butanol, butanediol, or a combination of at least two thereof.

[0026] Preferably, the mass ratio of the inorganic filler to the alcohol solvent is 1:10 to 1:80, for example, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, etc.

[0027] Preferably, the mass ratio of the inorganic filler to the silane coupling agent is 0.5:1 to 2:1, for example, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, etc.

[0028] Preferably, the inorganic filler further includes a drying step before use.

[0029] Preferably, the temperature is increased to 40-75°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, etc.

[0030] Preferably, the reaction time is 2 to 5 h, for example, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc.

[0031] As a preferred technical solution of the present invention, a suitable inorganic filler is used and a silane coupling agent is used to modify its surface, thereby improving the compatibility of the inorganic filler with dicyclopentadiene, thereby enhancing the dispersibility and stability of the inorganic filler, thereby solving the problem of sedimentation and stratification of the inorganic filler in the dicyclopentadiene system. For the same inorganic filler, the stability retention time of the inorganic filler without surface modification in the dicyclopentadiene liquid is 3-7 hours; the stability retention time of the inorganic filler with surface modification in the dicyclopentadiene liquid is 3 days.

[0032] Preferably, the melt index of the polymer resin is 6 to 30 g / min, for example 6 g / min, 8 g / min, 10 g / min, 13 g / min, 15 g / min, 18 g / min, 20 g / min, 23 g / min, 25 g / min, 28 g / min, 30 g / min, etc.

[0033] Preferably, the polymer resin includes styrene-butadiene block copolymer (SBS), hydrogenated styrene-butadiene block copolymer (SEBS), polybutadiene, styrene-maleic anhydride copolymer (SMA), polyolefin elastomer (POE), ethylene-vinyl acetate resin (EVA), ethylene-vinyl acetate copolymer (EVM), styrene-isoprene-styrene copolymer (SIS) and any one or at least two combinations of SBS, SEBS (such as: SBS of star configuration) of different configurations. The present invention uses suitable polymer resins to be dissolved in dicyclopentadiene, increase the viscosity of dicyclopentadiene feed liquid, so as to strengthen the dispersibility and stability of inorganic fillers in dicyclopentadiene feed liquid, so that inorganic fillers are dispersed in dicyclopentadiene to reach uniformity and stability, meet the requirements of reaction injection molding process, dicyclopentadiene feed liquid modified by polymer resin, surface modified inorganic filler stability retention time is greater than 45 days, can reach industrial production and use requirements.

[0034] Preferably, the styrene-butadiene block copolymer can be American Kraton: D-5119, D4158K, D-1101BM; Huizhou Li Changrong: 3501, 3520, 3522, 3540; TSRC: 3206, 4202, 4230, etc.

[0035] Preferably, the hydrogenated styrene-butadiene block copolymer can be American Kraton: G1652, G1650, G1701, G1654, G-1651; Taiwan Rubber: 6151, 6154, 6159; Baling Petrochemical: YH503, YH561, YH602, YH604, etc.

[0036] Preferably, the catalyst comprises a ruthenium metal catalyst (such as ruthenium metal complexes Grubbs II, Grubbs III, Hoveyda-Grubbs, Hoveyda-Grubbs II, homemade Grubbs catalyst, etc.) and / or a tungsten-molybdenum metal catalyst.

[0037] Preferably, the raw materials for preparing the inorganic enhanced polydicyclopentadiene material may also include a promoter.

[0038] Preferably, the co-catalyst includes any one of benzophenone, triphenylphosphine, triethyl phosphite, diethyl phosphite, trimethyl phosphate, and p-methylphenol, or a combination of at least two thereof.

[0039] In the present invention, by adjusting the use ratio of polymer resin, the use ratio of surface modified inorganic filler and the surface modification ratio of silane coupling agent in surface modified inorganic filler, inorganic reinforced polydicyclopentadiene feed liquid with uniform distribution of inorganic filler can be obtained, and the mechanical properties of polydicyclopentadiene can be adjusted. In the present invention, each functional auxiliary agent can be added according to any proportion, and a solution with uniformity and stability is obtained, so that the mechanical properties of dicyclopentadiene feed liquid can be adjusted. Because the obtained dicyclopentadiene feed liquid is a solution with uniformity and stability, the reaction injection molding process requirements are met, and industrialized production can be achieved.

[0040] In a second aspect, the present invention provides a method for preparing the inorganic enhanced polydicyclopentadiene material as described in the first aspect, the preparation method comprising the following steps:

[0041] The formulated amount of dicyclopentadiene and polymer resin are mixed, heated, and efficiently sheared, and then a surface-modified inorganic filler is added, and the shearing is continued. Thereafter, a catalyst is added, and the mixture is cured to obtain the inorganic reinforced polydicyclopentadiene material.

[0042] Preferably, the temperature is increased to 30-75°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, etc.

[0043] Preferably, the shearing time is 2 to 5 h, for example, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, etc.

[0044] Preferably, the continued shearing time is 1 to 4 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc.

[0045] Preferably, the curing temperature is 45-100°C, for example, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, etc., and the curing time is 2-5h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc.

[0046] In a third aspect, the present invention provides an application of the inorganic reinforced polydicyclopentadiene material as described in the first aspect in rail transit, agricultural machinery, and transportation industry.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] In the present invention, the raw materials for preparing the polydicyclopentadiene material include both surface-modified inorganic fillers and polymer resins, which work synergistically to effectively solve the problem of easy sedimentation and stratification of the inorganic filler in the dicyclopentadiene liquid, and the problem of poor surface compatibility between the inorganic filler and the polydicyclopentadiene material, and at the same time, the adverse effect of using a surface coupling agent on the performance of the polydicyclopentadiene material can be avoided. The inorganic filler-reinforced dicyclopentadiene liquid prepared by the present invention can meet the requirements of the reaction injection molding process. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 The initial state diagrams are of the solution prepared from the feed liquid provided in Example 1 (liquid A) and the solution prepared from the feed liquid provided in Comparative Example 1 (liquid B).

[0050] Figure 2 The state diagram of the solution prepared from the feed liquid provided in Example 1 (liquid A) and the solution prepared from the feed liquid provided in Comparative Example 1 (liquid B) after standing for 7 days.

[0051] Figure 3 The state diagram of the solution prepared from the feed liquid provided in Example 1 (liquid A) and the solution prepared from the feed liquid provided in Comparative Example 1 (liquid B) after standing for 45 days. DETAILED DESCRIPTION

[0052] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0053] Preparation Example 1

[0054] In this preparation example, a calcium carbonate whose surface is modified by a silane coupling agent is provided, and the preparation method comprises the following steps:

[0055] Mix the dried calcium carbonate (average particle size of 20 nm) with ethanol, gradually heat up to 50° C., then gradually add a silane coupling agent (vinyl silane coupling agent, vinyl triethoxysilane A151) dropwise, react for 3 hours, and after the reaction is completed, cool to room temperature, remove the solvent, and dry to obtain the calcium carbonate whose surface is modified by the silane coupling agent;

[0056] Among them, the mass ratio of calcium carbonate to ethanol is 1:20, and the mass ratio of calcium carbonate to silane coupling agent is 1:1.

[0057] Preparation Example 2

[0058] In this preparation example, an aluminum hydroxide whose surface is modified by a silane coupling agent is provided, and the preparation method comprises the following steps:

[0059] The dried aluminum hydroxide (average particle size of 50 nm) was mixed with ethanol, and the temperature was gradually raised to 60° C., and then a silane coupling agent (epoxy silane coupling agent: γ-glycidyloxypropyltrimethoxysilane KH560) was gradually added dropwise, and the reaction was performed for 4 hours. After the reaction was completed, the temperature was cooled to room temperature, the solvent was removed, and the mixture was dried to obtain the aluminum hydroxide whose surface was modified by the silane coupling agent;

[0060] Among them, the mass ratio of aluminum hydroxide to ethanol is 1:70, and the mass ratio of aluminum hydroxide to silane coupling agent is 1.5:1.

[0061] Unless otherwise specified, some of the raw material information used in the following embodiments of the present invention is as follows:

[0062] Styrene-butadiene block copolymer: Kraton, USA: D-5119.

[0063] Hydrogenated styrene-butadiene block copolymer: Baling Petrochemical: YH503.

[0064] Ruthenium metal complex: Grubbs II.

[0065] Example 1

[0066] In this embodiment, an inorganic enhanced polydicyclopentadiene material is provided. The raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

[0067]

[0068] The surface-modified inorganic filler is calcium carbonate modified by a silane coupling agent (provided in Preparation Example 1), the polymer resin is a styrene-butadiene block copolymer, and the catalyst is a ruthenium metal complex.

[0069] The preparation method comprises the following steps:

[0070] (1) Adding polymer resin to cyclopentadiene, heating to 75°C, and high-efficiency shearing for 3 hours to obtain a clear and transparent solution, cooling to room temperature, and setting aside;

[0071] (2) adding the surface-modified inorganic filler to the solution obtained in step (1), subjecting the solution to high-efficiency shearing for 2 hours to obtain a uniform and stable solution, and allowing the solution to stand for use after degassing;

[0072] (3) Adding a catalyst to the solution obtained in step (2), mechanically stirring, mixing thoroughly, injecting the mixed liquid into a mold, and curing at 80° C. for 5 h to obtain an inorganic reinforced polydicyclopentadiene material sample.

[0073] Example 2

[0074] In this embodiment, an inorganic enhanced polydicyclopentadiene material is provided. The raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

[0075]

[0076] Wherein, the surface-modified inorganic filler is aluminum hydroxide (provided by Preparation Example 2) whose surface is modified by a silane coupling agent, the polymer resin is a styrene-butadiene block copolymer, and the catalyst is a ruthenium metal complex.

[0077] The preparation method comprises the following steps:

[0078] (1) Adding polymer resin to cyclopentadiene, heating to 75°C, and high-efficiency shearing for 3 hours to obtain a clear and transparent solution, cooling to room temperature, and setting aside;

[0079] (2) adding the surface-modified inorganic filler to the solution obtained in step (1), subjecting the solution to high-efficiency shearing for 3 hours to obtain a uniform and stable solution, and allowing the solution to stand for use after degassing;

[0080] (3) Adding a catalyst to the solution obtained in step (2), mechanically stirring, mixing thoroughly, injecting the mixed liquid into a mold, and curing at 85° C. for 4 hours to obtain an inorganic reinforced polydicyclopentadiene material sample.

[0081] Example 3

[0082] In this embodiment, an inorganic enhanced polydicyclopentadiene material is provided. The raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

[0083]

[0084] The surface-modified inorganic filler is calcium carbonate modified by a silane coupling agent (provided in Preparation Example 1), the polymer resin is a hydrogenated styrene-butadiene block copolymer, and the catalyst is a ruthenium metal complex.

[0085] The preparation method comprises the following steps:

[0086] (1) Adding a polymer resin to cyclopentadiene, heating to 65° C., and subjecting to high-efficiency shearing for 4 h to obtain a clear and transparent solution, cooling to room temperature, and setting aside;

[0087] (2) adding the surface-modified inorganic filler to the solution obtained in step (1), subjecting the solution to high-efficiency shearing for 2 hours to obtain a uniform and stable solution, and allowing the solution to stand for use after degassing;

[0088] (3) Adding a catalyst to the solution obtained in step (2), mechanically stirring, mixing thoroughly, injecting the mixed liquid into a mold, and curing at 90° C. for 3 h to obtain an inorganic reinforced polydicyclopentadiene material sample.

[0089] Example 4

[0090] In this embodiment, an inorganic enhanced polydicyclopentadiene material is provided. The raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

[0091]

[0092] The surface-modified inorganic filler is aluminum hydroxide (provided in Preparation Example 2) whose surface is modified by a silane coupling agent, the polymer resin is a hydrogenated styrene-butadiene block copolymer, and the catalyst is a ruthenium metal complex.

[0093] The preparation method comprises the following steps:

[0094] (1) Adding a polymer resin to cyclopentadiene, heating to 65° C., and subjecting to high-efficiency shearing for 4 h to obtain a clear and transparent solution, cooling to room temperature, and setting aside;

[0095] (2) adding the surface-modified inorganic filler to the solution obtained in step (1), subjecting the solution to high-efficiency shearing for 1 hour to obtain a uniform and stable solution, and allowing the solution to stand for use after degassing;

[0096] (3) Adding a catalyst to the solution obtained in step (2), mechanically stirring, mixing thoroughly, injecting the mixed liquid into a mold, and curing at 95° C. for 2 h to obtain an inorganic reinforced polydicyclopentadiene material sample.

[0097] Comparative Example 1

[0098] In this comparative example, a polydicyclopentadiene material is provided. The raw materials for preparing the polydicyclopentadiene material include the following components in parts by weight:

[0099] 99.9 parts of dicyclopentadiene;

[0100] 0.1 part of catalyst;

[0101] Wherein, the catalyst is a ruthenium metal complex.

[0102] The preparation method comprises the following steps:

[0103] The dicyclopentadiene and the catalyst were fully mixed, the mixed liquid was injected into a mold, and cured at 80° C. for 5 hours to obtain a polydicyclopentadiene material sample.

[0104] Comparative Example 2

[0105] In this comparative example, a polydicyclopentadiene material is provided. The raw materials for preparing the polydicyclopentadiene material include the following components in parts by weight:

[0106] 98.9 parts of dicyclopentadiene;

[0107] 1 part of polymer resin;

[0108] 0.1 part of catalyst;

[0109] The polymer resin is a styrene-butadiene block copolymer, and the catalyst is a ruthenium metal complex.

[0110] The preparation method comprises the following steps:

[0111] (1) Adding polymer resin to cyclopentadiene, heating to 75°C, and high-efficiency shearing for 3 hours to obtain a clear and transparent solution, cooling to room temperature, and setting aside;

[0112] (2) Adding a catalyst to the solution obtained in step (1), mechanically stirring, mixing thoroughly, injecting the mixed liquid into a mold, and curing at 80° C. for 5 h to obtain a polydicyclopentadiene material sample.

[0113] Comparative Example 3

[0114] In this comparative example, an inorganic enhanced polydicyclopentadiene material is provided. The raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

[0115] 96.9 parts of dicyclopentadiene;

[0116] 3 parts of surface modified inorganic filler;

[0117] 0.1 part of catalyst;

[0118] Wherein, the surface-modified inorganic filler is calcium carbonate modified by a silane coupling agent (provided in Preparation Example 1), and the catalyst is a ruthenium metal complex.

[0119] The preparation method comprises the following steps:

[0120] (1) adding the surface-modified inorganic filler into dicyclopentadiene, subjecting it to high-efficiency shearing for 2 hours to obtain a uniform and stable solution, and then allowing it to stand and degas for later use;

[0121] (2) Adding a catalyst to the solution obtained in step (1), mechanically stirring, and mixing thoroughly, injecting the mixed liquid into a mold, and curing at 80° C. for 5 h to obtain an inorganic reinforced polydicyclopentadiene material sample.

[0122] The dicyclopentadiene feed solution provided in Example 1 of the present invention and Comparative Example 1 was subjected to a stability test, and the method was as follows:

[0123] Carbon black was added to the dicyclopentadiene feed solutions provided in Example 1 and Comparative Example 1 (i.e., the solution obtained in step (2)), and the prepared solutions were poured into glass test tubes. The test tubes were placed on a test tube rack to examine the stability of the feed solutions. The solution prepared by the feed solution provided in Example 1 was recorded as A solution, and the solution prepared by the feed solution provided in Comparative Example 1 was recorded as B solution. The initial state diagram of A solution and B solution, the state diagram after standing for 7 days, and the state diagram after standing for 45 days are shown in Figures 1 and 2. Figure 1-Figure 3 It can be seen that the present invention effectively solves the problem that the inorganic filler is easy to settle and delaminate in the dicyclopentadiene liquid.

[0124] The polydicyclopentadiene material samples provided in the embodiments of the present invention and the comparative examples were processed to obtain specimens that meet the polydicyclopentadiene resin performance test, and mechanical properties tests were carried out. The test method is as follows:

[0125] (1) Tensile strength and tensile modulus: tested in accordance with GB / T 2567-2021;

[0126] (2) Flexural strength and flexural modulus: tested in accordance with GB / T 2567-2021.

[0127] The performance test results are shown in Table 1.

[0128] Table 1

[0129] Tensile strength / MPa Tensile modulus / MPa Bending strength / MPa Flexural modulus / MPa Example 1 63.28 2731 87.36 2841 Example 2 58.68 2545 90.02 2634 Example 3 55.92 2642 80.99 2563 Example 4 54.13 2381 83.07 2502 Comparative Example 1 37.80 1751 68.36 1629 Comparative Example 2 40.31 1704 64.75 1640 Comparative Example 3 43.89 2109 75.67 2205

[0130] It can be seen from Table 1 that the polydicyclopentadiene materials provided in the embodiments of the present invention have higher tensile strength (54.13-63.28 MPa), higher tensile modulus (2381-2731 MPa), higher flexural strength (80.99-90.02 MPa), and higher flexural modulus (2502-2841 MPa).

[0131] Preferably, compared with Example 1, the mechanical properties of the polydicyclopentadiene materials provided in Comparative Examples 1-3 are significantly reduced.

[0132] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the inorganic reinforced polydicyclopentadiene material and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An inorganic reinforced polydicyclopentadiene material, characterized in that: The raw materials for preparing the inorganic enhanced polydicyclopentadiene material include the following components in parts by weight:

2. The inorganic enhanced polydicyclopentadiene material according to claim 1, characterized in that: The surface-modified inorganic filler includes an inorganic filler whose surface is modified by a silane coupling agent; Preferably, the silane coupling agent includes any one of an alkyl silane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent, a silane polymer, an amino silane, and a phenyl silane, or a combination of at least two thereof; Preferably, the inorganic filler includes any one of white carbon black, calcium carbonate, aluminum hydroxide, silicon dioxide, and carbon black, or a combination of at least two thereof; Preferably, the particle size of the inorganic filler is 1 to 100 nm.

3. The inorganic reinforced polydicyclopentadiene material according to claim 1 or 2, characterized in that: The surface modified inorganic filler is prepared by the following method: The inorganic filler is mixed with an alcohol solvent, heated, then a silane coupling agent is added, reacted, the alcohol solvent is removed, and dried to obtain the surface-modified inorganic filler.

4. The inorganic reinforced polydicyclopentadiene material according to claim 3, characterized in that: The alcohol solvent includes any one of methanol, ethanol, butanol, butanediol, or a combination of at least two thereof; Preferably, the mass ratio of the inorganic filler to the alcohol solvent is 1:10 to 1:80; Preferably, the mass ratio of the inorganic filler to the silane coupling agent is 0.5:1 to 2:1; Preferably, the inorganic filler further comprises a drying step before use; Preferably, the temperature is raised to 40-75°C; Preferably, the reaction time is 2 to 5 hours.

5. The inorganic reinforced polydicyclopentadiene material according to any one of claims 1 to 4, characterized in that: The melt index of the polymer resin is 6 to 30 g / min.

6. The inorganic reinforced polydicyclopentadiene material according to any one of claims 1 to 5, characterized in that: The polymer resin includes any one of styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, polybutadiene, styrene-maleic anhydride copolymer, polyolefin elastomer, ethylene-vinyl acetate resin, ethylene-vinyl acetate copolymer, styrene-isoprene-styrene copolymer or a combination of at least two thereof.

7. The inorganic reinforced polydicyclopentadiene material according to any one of claims 1 to 6, characterized in that: The catalyst includes a ruthenium metal catalyst and / or a tungsten-molybdenum metal catalyst.

8. A method for preparing an inorganic enhanced polydicyclopentadiene material as claimed in any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The formulated amount of dicyclopentadiene and polymer resin are mixed, heated, sheared, and then a surface-modified inorganic filler is added, the shearing is continued, and then a catalyst is added and cured to obtain the inorganic reinforced polydicyclopentadiene material.

9. The preparation method according to claim 8, characterized in that: The heating is to 30-75°C; Preferably, the shearing time is 2 to 5 hours; Preferably, the continued shearing time is 1 to 4 hours; Preferably, the curing temperature is 45-100° C. and the curing time is 2-5 hours.

10. Use of the inorganic enhanced polydicyclopentadiene material according to any one of claims 1 to 7 in rail transportation, agricultural machinery and transportation industry.

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