Thermosetting composite materials and their preparation methods

Abstract

This invention provides a thermosetting composite material and its preparation method, belonging to the field of polymer material synthesis technology. The thermosetting composite material includes: a thermosetting material obtained by metathesis copolymerization of a cyclic olefin monomer and a comonomer, and a filler material embedded inside the thermosetting material during the metathesis copolymerization process; wherein, the comonomer is selected from norbornene derivatives or tricyclopentadiene, and the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters; the cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; and the filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis technology, and particularly relates to a thermosetting composite material and its preparation method, and more specifically to an enhanced thermosetting composite material and its preparation method. Background Technology

[0002] Polydicyclopentadiene (PDCPD) is a thermosetting engineering plastic with good comprehensive mechanical properties, as well as good dimensional stability, acid and alkali resistance, excellent coating and electrical insulation properties. It has wide applications in transportation, chemical industry, electrical equipment, sports equipment and other fields. However, there is still room for improvement in the mechanical properties of PDCPD materials. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a thermosetting composite material and its preparation method, aiming to at least partially solve the technical problem that existing polymer materials cannot meet diverse needs. The technical solution provided by this invention is as follows.

[0004] As a first aspect of the present invention, a thermosetting composite material is provided, comprising: a thermosetting material obtained by metathesis copolymerization of a cyclic olefin monomer and a comonomer, and a filler material embedded within the thermosetting material during the metathesis copolymerization process; wherein the comonomer is selected from norbornene derivatives or tricyclopentadiene, the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters; the cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; and the filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

[0005] As a second aspect of the present invention, a method for preparing a thermosetting composite material is provided, comprising: uniformly mixing a cyclic olefin monomer, a comonomer, a metathesis catalyst, and a filler material; and, during a heating and curing process, the cyclic olefin monomer and the comonomer undergo a metathesis copolymerization reaction under the action of the metathesis catalyst to obtain a thermosetting material, wherein the filler material is embedded inside the thermosetting material to obtain a thermosetting composite material; wherein the comonomer is selected from norbornene derivatives or tricyclopentadiene, and the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters; the cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; and the filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

[0006] In this invention, cyclic olefin monomers (such as dicyclopentadiene or norbornene) undergo metathesis copolymerization with tricyclopentadiene or norbornene derivatives with different polar groups in the presence of a filler material (such as glass fiber or carbon fiber). During the metathesis copolymerization process, the filler material is embedded into the thermosetting material, and after curing, a thermosetting composite material is formed. The preparation process of the thermosetting composite material of this invention is simple and easy to control, and a series of thermosetting composite materials with excellent tensile and flexural properties can be prepared to meet the needs of different application scenarios. Attached Figure Description

[0007] Figure 1 Tensile diagrams of different thermosetting composite materials in Examples 1-4 of the present invention are shown, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 1, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-CF prepared in Example 2, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-CF prepared in Example 3, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-CF prepared in Example 4;

[0008] Figure 2 Tensile diagrams of different thermosetting composite materials in Examples 5-8 of the present invention are shown, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 5, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-GF prepared in Example 6, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-GF prepared in Example 7, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-GF prepared in Example 8;

[0009] Figure 3 The images show bending diagrams of different thermosetting composite materials in Examples 9-12 of the present invention, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 9, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-CF prepared in Example 10, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-CF prepared in Example 11, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-CF prepared in Example 12;

[0010] Figure 4The images show bending diagrams of different thermosetting composite materials in Examples 13-16 of the present invention, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 13, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-GF prepared in Example 14, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-GF prepared in Example 15, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-GF prepared in Example 16;

[0011] Figure 5 Tensile diagrams of different thermosetting composite materials in Examples 17-18 and Comparative Example 5 of the present invention are shown, wherein (a) is PDCPD-B1-1 / 3 / 9 / 15 / 30% prepared in Comparative Example 5, (b) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 17, and (c) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 3;

[0012] Figure 6 The images show the bending diagrams of different thermosetting composite materials in Examples 19-20 and Comparative Example 6 of the present invention, where (a) is PDCPD-B1-1 / 3 / 9 / 15 / 30% prepared in Comparative Example 6, (b) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 19, and (c) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 20. Detailed Implementation

[0013] Polydicyclopentadiene has a wide range of applications, but its performance still needs to be further improved. This invention proposes to use norbornene derivatives or tricyclopentadiene containing different polar groups to carry out metathesis copolymerization reaction with cyclic olefin monomers under the action of metathesis catalyst, and mix them evenly with filler materials to obtain thermosetting composite materials, so as to enhance the mechanical properties of thermosetting materials by using filler materials, norbornene derivatives or tricyclopentadiene.

[0014] Specifically, as a first aspect of the present invention, a thermosetting composite material is provided, comprising: a thermosetting material obtained by metathesis copolymerization of a cyclic olefin monomer and a comonomer, and a filler material embedded within the thermosetting material during the metathesis copolymerization process; wherein the comonomer is selected from norbornene derivatives or tricyclopentadiene, the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters; the cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; and the filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

[0015] In this invention, dicyclopentadiene and / or norbornene are used as cyclic olefin monomer raw materials, and tricyclopentadiene or norbornene derivatives containing different polar groups are used as comonomer raw materials. Both have similar structures and high compatibility, allowing for uniform mixing during the preparation of thermosetting materials. Furthermore, the norbornene derivatives containing polar groups exhibit good compatibility with the filler material and can interact with the surface of the filler material during metathesis copolymerization. After metathesis copolymerization, a series of thermosetting composite materials with different polar groups are prepared. The copolymerization of norbornene derivatives with dicyclopentadiene exhibits higher mechanical properties compared to polydicyclopentadiene or polynorbornene. Introducing polar groups into the copolymerization reaction of norbornene derivatives and dicyclopentadiene can form a denser three-dimensional network structure and a more tightly integrated bond with the filler material. While retaining the structure and excellent mechanical properties of polydicyclopentadiene and / or polynorbornene, this avoids problems such as uneven dispersion and agglomeration of the filler material, enhancing the mechanical and processing properties of thermosetting composites and improving the surface polarity of thermosetting materials. By controlling the type of norbornene derivative and the selection of filler materials, the thermosetting composite material of this invention can obtain thermosetting composites with different strengths and toughnesses, solving the problem that current polymer composites cannot meet diverse needs and has broad application prospects. Tricyclopentadiene has a similar structure to dicyclopentadiene or norbornene, exhibiting high compatibility. After metathesis copolymerization, thermosetting composites with excellent tensile or flexural properties can be obtained.

[0016] According to embodiments of the present invention, the cyclic olefin monomer is preferably dicyclopentadiene because the dicyclopentadiene molecule contains two fused cyclopentenes. After copolymerization with norbornene derivatives, dicyclopentadiene can form a more rigid three-dimensional network structure, thereby having higher mechanical properties.

[0017] According to embodiments of the present invention, the norbornene derivative is selected from at least one of 5-norbornene-2-methanol, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylic acid, and 5-norbornene-2-yl acetate. The aforementioned norbornene derivatives contain hydroxyl (-OH), carboxyl (-COOH), and ester groups, respectively. The presence of these polar groups can enhance the degree of crosslinking between the cyclic olefin monomer and the norbornene derivative, thereby improving the mechanical properties of the thermosetting material. At the same time, the presence of polar groups can interact with the surface groups of the filler material, improving the compatibility between the thermosetting material and the filler material, thereby enhancing the mechanical properties of the thermosetting material using the filler material.

[0018] According to embodiments of the present invention, by using different norbornene derivatives and controlling their dosage while employing the same filler material, thermosetting composite materials with different tensile and flexural properties can be obtained to meet the diverse needs of thermosetting composite materials. For example, in some embodiments, the norbornene derivative is preferably selected from at least one of 5-norbornene-2-methanol and 5-norbornene-2-carboxylic acid.

[0019] According to embodiments of the present invention, the molar ratio of norbornene derivative to cycloolefin monomer is 1-30:100, for example: 1:100 (i.e., 1%), 5:100 (i.e., 5%), 10:100 (i.e., 10%), 15:100 (i.e., 15%), 20:100 (i.e., 20%), 25:100 (i.e., 25%), 30:100 (i.e., 30%). For example, the molar ratio of norbornene derivative to dicyclopentadiene is 1-30:100. Within this range, as the amount of norbornene derivative increases, the mechanical properties of the thermosetting composite material, such as tensile strength, tensile toughness, and flexural strength, can be appropriately enhanced. Similarly, the molar ratio of tricyclopentadiene to cycloolefin monomers can be 1-30:100, for example: 1:100 (1%), 5:100 (5%), 10:100 (10%), 15:100 (15%), 20:100 (20%), 25:100 (25%), and 30:100 (30%). For example, the molar ratio of tricyclopentadiene to dicyclopentadiene can be 1-30:100. Within this range, increasing the amount of tricyclopentadiene can appropriately increase the tensile properties of thermosetting materials and thermosetting composites. The combination of tricyclopentadiene with fillers can further improve the performance of thermosetting composites.

[0020] According to embodiments of the present invention, the filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black or silica, wherein glass fiber (GF) or carbon fiber (CF) is more preferred.

[0021] According to embodiments of the present invention, the amount of filler added is 3%-17% of the total mass of the comonomer and cycloolefin monomer, for example, it can be 3%, 5%, 7%, 9%, 10%, 12%, 14%, 15%, 17%, etc., or any value within this range. With the increase of filler, the tensile strength and other properties of the thermosetting composite material gradually increase, while the flexural strength gradually decreases.

[0022] According to embodiments of the present invention, in terms of improving mechanical properties, carbon fiber or glass fiber is preferably used as long fiber compared to short fiber, with a length of 70-90 mm and a diameter of 10 μm-15 μm, for example, the long fiber has a length of 80 mm and a diameter of 14 μm.

[0023] According to embodiments of the present invention, the norbornene derivatives, tricyclopentadiene, and cyclic olefin monomers used are all commercially available.

[0024] As a second aspect of the present invention, a method for preparing a thermosetting composite material is provided, comprising: uniformly mixing a cyclic olefin monomer, a comonomer, a metathesis catalyst, and a filler material; and, during a heating and curing process, the cyclic olefin monomer and the comonomer undergo a metathesis copolymerization reaction under the action of the metathesis catalyst to obtain a thermosetting material, wherein the filler material is embedded inside the thermosetting material to obtain a thermosetting composite material; wherein the comonomer is selected from norbornene derivatives or tricyclopentadiene, and the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters; the cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; and the filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

[0025] In this invention, norbornene derivatives or tricyclopentadiene containing different polar groups are mixed uniformly with cyclic olefin monomers, and a metathesis catalyst is added and mixed uniformly again to obtain a mixture. The mixture is injected into a mold lined with a filler material, and the mixture and filler material are mixed uniformly. During the heating and curing process, under the catalysis of the metathesis catalyst, the cyclic olefin monomers and comonomers undergo metathesis reaction to form a thermosetting material. At the same time, the filler material is embedded into the thermosetting material, resulting in a thermosetting composite material reinforced with norbornene derivatives or tricyclopentadiene. The preparation method of this thermosetting composite material is relatively simple, does not use any organic solvents, the reaction is easy to control, and the prepared thermosetting composite material has excellent mechanical properties, such as tensile and flexural properties, which can effectively solve the problem that the current preparation of polymer materials cannot meet diverse needs.

[0026] Specifically, the method for preparing thermosetting composite materials according to the present invention includes: melting and uniformly mixing norbornene derivatives and cyclic olefin monomers, adding a metathesis catalyst to obtain a mixture; injecting the mixture into a mold lined with filler material, and undergoing a metathesis copolymerization reaction during heating and curing to obtain a thermosetting composite material. The molar ratio of norbornene derivatives or tricyclopentadiene to cyclic olefin monomers is 1-30:100, and the metathesis catalyst is selected from tungsten-based catalysts or ruthenium-based carbene catalysts, wherein the ruthenium-based carbene catalyst is a Grubbs second-generation catalyst (GII for short), and the amount of the metathesis catalyst is 0.1%-0.5% of the total molar amount of the comonomers (norbornene derivatives or tricyclopentadiene) and cyclic olefin monomers, preferably 0.1%. The temperature during the heat curing process is 80-160℃, for example, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, and 160℃; the heat curing time is 30min-2h, for example, 30min, 50min, 60min, 90min, and 120min. Within this temperature and time period, the metathesis catalyst catalyzes the polymerization reaction of the comonomer (norbornene derivative or tricyclopentadiene) and cyclic olefin monomers to form a thermosetting material. Simultaneously, the thermosetting material reacts with the filler material spread in the mold, causing the filler material to embed into the interior of the thermosetting material, forming a tightly cross-linked thermosetting composite material. This further improves the mechanical properties of the material and prevents the filler material from precipitating or separating during use.

[0027] According to embodiments of the present invention, the norbornene derivative-reinforced thermosetting composite material prepared by the method of the present invention has the following repeating unit structure:

[0028] .

[0029] According to an embodiment of the present invention, the tricyclopentadiene-reinforced thermosetting composite material prepared by the method of the present invention has the following repeating unit structure, wherein n is n=0-5, representing the number of norbornene groups in the comonomer.

[0030] .

[0031] The technical solutions of the present invention will be described in detail below with reference to specific embodiments. However, it should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the invention. In the following detailed description, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present invention for ease of explanation. However, it will be apparent that one or more embodiments may be implemented without these specific details. Furthermore, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessarily obscuring the concepts of the present invention.

[0032] It should be noted that the raw materials used in this invention can be commercially available or synthesized using known methods.

[0033] Tensile property testing: According to the standard test method ASTM 638, the specimen is a dumbbell-shaped strip with a length of 25 mm, a width of 2 mm (at its narrowest point), and a thickness of 0.5 mm; and stress / strain tests are conducted at room temperature at a speed of 10 cm / min.

[0034] Bending performance test: According to the standard test method GB / T 9341-2008, the specimen is a strip with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The bending strength and bending stress-strain relationship are determined by a three-point loading test (free support at both ends and loading at the center).

[0035] Example 1

[0036] Dicyclopentadiene (DCPD) and 5-norbornene-2-methanol (A1) were melted separately (at 50°C) and then mixed at molar ratios of A1 to DCPD of 1:100, 3:100, 9:100, 15:100, and 30:100. Subsequently, Grubbs second-generation catalyst (GII, at 0.1% of the total molar amount of DCPD and A1) was added, and the mixture was rapidly stirred at 400 rpm until homogeneous to obtain the final mixture. The mixture was injected into a polytetrafluoroethylene stretching mold filled with carbon fiber (CF, fiber length 80 mm, diameter 14 μm), and the mold was placed in an oven at 140℃ for 30 min to cure. After cooling and demolding, thermosetting composite materials were obtained, which were labeled as PDCPD-A1-1%-CF, PDCPD-A1-3%-CF, PDCPD-A1-9%-CF, PDCPD-A1-15%-CF, and PDCPD-A1-30%-CF, respectively.

[0037] Example 2

[0038] Thermosetting composite materials were prepared using the same method as in Example 1, except that 5-norbornene-2-carboxylic acid (A2) and dicyclopentadiene (DCPD) were mixed in molar ratios of 1:100, 3:100, 9:100, 15:100, and 30:100, respectively. The resulting thermosetting composite materials were labeled as PDCPD-A2-1%-CF, PDCPD-A2-3%-CF, PDCPD-A2-9%-CF, PDCPD-A2-15%-CF, and PDCPD-A2-30%-CF, respectively.

[0039] Example 3

[0040] Thermosetting composite materials were prepared using the same method as in Example 1, except that methyl 5-norbornene-2-carboxylate (A3) and dicyclopentadiene (DCPD) were mixed in molar ratios of 1:100, 3:100, 9:100, 15:100, and 30:100, respectively. The resulting thermosetting composite materials were labeled as PDCPD-A3-1%-CF, PDCPD-A3-3%-CF, PDCPD-A3-9%-CF, PDCPD-A3-15%-CF, and PDCPD-A3-30%-CF, respectively.

[0041] Example 4

[0042] Thermosetting composite materials were prepared using the same method as in Example 1, except that 5-norberne-2-ylacetate (A4) and dicyclopentadiene (DCPD) were mixed in molar ratios of 1:100, 3:100, 9:100, 15:100, and 30:100, respectively. The resulting thermosetting composite materials were labeled as PDCPD-A4-1%-CF, PDCPD-A4-3%-CF, PDCPD-A4-9%-CF, PDCPD-A4-15%-CF, and PDCPD-A4-30%-CF, respectively.

[0043] Example 5

[0044] Thermosetting composite materials were prepared using the same method as in Example 1, except that carbon fiber (CF) was replaced with long glass fiber (GF) with a length of 80 mm and a diameter of 14 μm. The resulting thermosetting composite materials were labeled as PDCPD-A1-1%-GF, PDCPD-A1-3%-GF, PDCPD-A1-9%-GF, PDCPD-A1-15%-GF, and PDCPD-A1-30%-GF, respectively.

[0045] Example 6

[0046] Thermosetting composite materials were prepared using the same method as in Example 2, except that carbon fiber (CF) was replaced with long glass fiber (GF) with a length of 80 mm and a diameter of 14 μm. The resulting thermosetting composite materials were labeled as PDCPD-A2-1%-GF, PDCPD-A2-3%-GF, PDCPD-A2-9%-GF, PDCPD-A2-15%-GF, and PDCPD-A2-30%-GF, respectively.

[0047] Example 7

[0048] Thermosetting composite materials were prepared using the same method as in Example 3, except that carbon fiber (CF) was replaced with long glass fiber (GF) with a length of 80 mm and a diameter of 14 μm. The resulting thermosetting composite materials were labeled as PDCPD-A3-1%-GF, PDCPD-A3-3%-GF, PDCPD-A3-9%-GF, PDCPD-A3-15%-GF, and PDCPD-A3-30%-GF, respectively.

[0049] Example 8

[0050] Thermosetting composite materials were prepared using the same method as in Example 4, except that carbon fiber (CF) was replaced with long glass fiber (GF) with a length of 80 mm and a diameter of 14 μm. The resulting thermosetting composite materials were labeled as PDCPD-A4-1%-GF, PDCPD-A4-3%-GF, PDCPD-A4-9%-GF, PDCPD-A4-15%-GF, and PDCPD-A4-30%-GF, respectively.

[0051] Example 9

[0052] Thermosetting composite materials were prepared using the same method as in Example 1, except that the mixture was injected into a polytetrafluoroethylene bending template filled with carbon fiber (CF) for bending performance testing.

[0053] Example 10

[0054] Thermosetting composite materials were prepared using the same method as in Example 2, except that the mixture was injected into a polytetrafluoroethylene bending template filled with carbon fiber (CF) for bending performance testing.

[0055] Example 11

[0056] Thermosetting composite materials were prepared using the same method as in Example 3, except that the mixture was injected into a polytetrafluoroethylene bending template filled with carbon fiber (CF) for bending performance testing.

[0057] Example 12

[0058] Thermosetting composite materials were prepared using the same method as in Example 4, except that the mixture was injected into a polytetrafluoroethylene bending template filled with carbon fiber (CF) for bending performance testing.

[0059] Example 13

[0060] Thermosetting composite materials were prepared using the same method as in Example 5, except that the mixture was injected into a polytetrafluoroethylene bending strip mold filled with long glass fibers (GF) for bending performance testing.

[0061] Example 14

[0062] Thermosetting composite materials were prepared using the same method as in Example 6, except that the mixture was injected into a polytetrafluoroethylene bending strip mold filled with long glass fibers (GF) for bending performance testing.

[0063] Example 15

[0064] Thermosetting composite materials were prepared using the same method as in Example 7, except that the mixture was injected into a polytetrafluoroethylene bending strip mold filled with long glass fibers (GF) for bending performance testing.

[0065] Example 16

[0066] Thermosetting composite materials were prepared using the same method as in Example 8, except that the mixture was injected into a polytetrafluoroethylene bending strip mold filled with long glass fibers (GF) for bending performance testing.

[0067] Comparative Example 1

[0068] After melting dicyclopentadiene (DCPD) at 50°C, Grubbs second-generation catalyst (GII, 1 mg) was added and stirred rapidly at 400 rpm to obtain a uniform mixture. This mixture was then injected into a polytetrafluoroethylene stretching mold filled with carbon fibers (CF, with a fiber length of 80 mm and a diameter of 14 μm). The mold was then placed in an oven at 140°C for curing for 30 min. After cooling and demolding, the resulting thermosetting composite material was labeled as PDCPD-CF.

[0069] Comparative Example 2

[0070] Thermosetting polydicyclopentadiene composite material was prepared using the same method as in Comparative Example 1, except that carbon fiber (CF) was replaced with long glass fiber (GF) with a length of 80 mm and a diameter of 14 μm. The resulting thermosetting composite material was labeled PDCPD-GF.

[0071] Comparative Example 3

[0072] The thermosetting polydicyclopentadiene composite material was prepared using the same method as in Comparative Example 1, except that the mixture was injected into a polytetrafluoroethylene bending strip mold filled with carbon fiber (CF) for bending performance testing.

[0073] Comparative Example 4

[0074] The thermosetting polydicyclopentadiene composite material was prepared using the same method as in Comparative Example 2, except that the mixture was injected into a polytetrafluoroethylene bending strip mold filled with glass fiber (GF) for bending performance testing.

[0075] The thermosetting composite materials prepared in Examples 1-16 and Comparative Examples 1-4 were subjected to tensile and flexural property tests, respectively. The specific test results are shown in Tables 1-4.

[0076] Table 1. Tensile properties of different thermosetting composite materials in Examples 1-4 and Comparative Example 1

[0077]

[0078] Table 2. Tensile properties of different thermosetting composite materials in Examples 5-8 and Comparative Example 2

[0079]

[0080] As shown in Tables 1 and 2, the use of filler materials and norbornene derivatives can significantly improve the tensile properties of polydicyclopentadiene, and the properties vary.

[0081] Table 3. Bending properties of different thermosetting composite materials in Examples 9-12 and Comparative Example 3

[0082]

[0083] Table 4. Bending properties of different thermosetting composite materials in Examples 13-16 and Comparative Example 4

[0084]

[0085] As shown in Tables 3 and 4, the use of filler materials and norbornene derivatives can significantly improve the flexural properties of polydicyclopentadiene.

[0086] Figure 1 Tensile diagrams of different thermosetting composite materials in Examples 1-4 of the present invention are shown, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 1, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-CF prepared in Example 2, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-CF prepared in Example 3, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-CF prepared in Example 4; Figure 2Tensile diagrams of different thermosetting composite materials in Examples 5-8 of the present invention are shown, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 5, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-GF prepared in Example 6, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-GF prepared in Example 7, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-GF prepared in Example 8.

[0087] like Figures 1-2 As shown, the thermosetting composite material reinforced with norbornene derivatives of the present invention has excellent tensile properties compared with thermosetting composite materials formed by polydicyclopentadiene.

[0088] Figure 3 The images show bending diagrams of different thermosetting composite materials in Examples 9-12 of the present invention, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 9, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-CF prepared in Example 10, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-CF prepared in Example 11, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-CF prepared in Example 12; Figure 4 The figures are bending diagrams of different thermosetting composite materials in Examples 13-16 of the present invention, wherein (a) is PDCPD-A1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 13, (b) is PDCPD-A2-1 / 3 / 9 / 15 / 30%-GF prepared in Example 14, (c) is PDCPD-A3-1 / 3 / 9 / 15 / 30%-GF prepared in Example 15, and (d) is PDCPD-A4-1 / 3 / 9 / 15 / 30%-GF prepared in Example 16.

[0089] like Figures 3-4 As shown, the thermosetting composite material reinforced with norbornene derivatives of the present invention has excellent bending properties compared with thermosetting composite materials formed by polydicyclopentadiene.

[0090] Comparative Example 5

[0091] Tricyclopentadiene (B1) and dicyclopentadiene (DCPD) were mixed at molar ratios of 1:100, 3:100, 9:100, 15:100, and 30:100. Then, Grubbs second-generation catalyst (GII, at 0.1% of the total molar amount of DCPD and B1) was added, and the mixture was rapidly stirred at 400 rpm until homogeneous, yielding a final mixture. This mixture was injected into a polytetrafluoroethylene (PTFE) stretching template mold. The mold was pre-cured in an oven at 35°C for 1 hour, then heated to 140°C for 30 minutes. After cooling and demolding, thermosetting composite materials were obtained, labeled as PDCPD-B1-1%, PDCPD-B1-3%, PDCPD-B1-9%, PDCPD-B1-15%, and PDCPD-B1-30%, respectively.

[0092] Example 17

[0093] Tricyclopentadiene (B1) and dicyclopentadiene (DCPD) were mixed at molar ratios of 1:100, 3:100, 9:100, 15:100, and 30:100. Then, Grubbs second-generation catalyst (GII, at 0.1% of the total molar amount of DCPD and B1) was added, and the mixture was rapidly stirred at 400 rpm until homogeneous, yielding the final mixture. The mixture was injected into a polytetrafluoroethylene (PTFE) tensile template mold filled with carbon fiber (CF, fiber length 80 mm, diameter 14 μm, addition amount 15%). The mold was first placed in an oven at 35℃ for pre-curing for 1 h, and then heated to 140℃ for curing for 30 min. After cooling and demolding, thermosetting composite materials were obtained, which were labeled as PDCPD-B1-1%-CF, PDCPD-B1-3%-CF, PDCPD-B1-9%-CF, PDCPD-B1-15%-CF, and PDCPD-B1-30%-CF, respectively.

[0094] Example 18

[0095] Tricyclopentadiene (B1) and dicyclopentadiene (DCPD) were mixed at molar ratios of 1:100, 3:100, 9:100, 15:100, and 30:100. Then, Grubbs second-generation catalyst (GII, at 0.1% of the total molar amount of DCPD and B1) was added, and the mixture was rapidly stirred at 400 rpm until homogeneous, yielding the final mixture. The mixture was injected into a polytetrafluoroethylene stretching template mold filled with glass fiber (GF, fiber length 80 mm, diameter 14 μm, addition amount 15%). The mold was first placed in an oven at 35℃ for pre-curing for 1 h, and then heated to 140℃ for curing for 30 min. After cooling and demolding, thermosetting composite materials were obtained, which were labeled as PDCPD-B1-1%-GF, PDCPD-B1-3%-GF, PDCPD-B1-9%-GF, PDCPD-B1-15%-GF, and PDCPD-B1-30%-GF, respectively.

[0096] Comparative Example 6

[0097] Thermosetting composite materials were prepared using the same method as in Comparative Example 5, except that the mixture was injected into a polytetrafluoroethylene bending template for bending performance testing.

[0098] Example 19

[0099] Thermosetting composite materials were prepared using the same method as in Example 17, except that the mixture was injected into a polytetrafluoroethylene bending template filled with carbon fiber (CF, fiber length 80 mm, diameter 14 μm, addition amount 6%) for bending performance testing.

[0100] Example 20

[0101] Thermosetting composite materials were prepared using the same method as in Example 18, except that the mixture was injected into a polytetrafluoroethylene bending template filled with carbon fiber (GF, fiber length 80 mm, diameter 14 μm, addition amount 6%) for bending performance testing.

[0102] The tensile properties of the thermosetting composite materials prepared in Examples 17-18 and Comparative Example 5 were tested respectively, and the specific test results are shown in Table 5.

[0103] Table 5. Tensile properties of different thermosetting composite materials in Examples 17-18 and Comparative Example 5

[0104]

[0105] As shown in Table 5, the tensile properties of polydicyclopentadiene can be significantly improved by using tricyclopentadiene and fillers.

[0106] The flexural properties of the thermosetting composite materials prepared in Examples 19-20 and Comparative Example 6 were tested, and the specific test results are shown in Table 6.

[0107] Table 6. Bending properties of different thermosetting composite materials in Examples 19-20 and Comparative Example 6

[0108]

[0109] As shown in Table 6, the flexural properties of polydicyclopentadiene can be significantly improved by using tricyclopentadiene and filler materials.

[0110] Figure 5 Tensile diagrams of different thermosetting composite materials in Examples 17-18 and Comparative Example 5 of the present invention are shown, wherein (a) is PDCPD-B1-1 / 3 / 9 / 15 / 30% prepared in Comparative Example 5, (b) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 17, and (c) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 3; Figure 6 The images show the bending diagrams of different thermosetting composite materials in Examples 19-20 and Comparative Example 6 of the present invention, where (a) is PDCPD-B1-1 / 3 / 9 / 15 / 30% prepared in Comparative Example 6, (b) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-CF prepared in Example 19, and (c) is PDCPD-B1-1 / 3 / 9 / 15 / 30%-GF prepared in Example 20.

[0111] like Figures 5-6 As shown, the thermosetting composite material of the present invention, reinforced with tricyclopentadiene and filler materials, has excellent tensile and flexural properties compared with thermosetting composite materials formed by polydicyclopentadiene.

[0112] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A thermosetting composite material, characterized in that, include: Thermosetting materials obtained by metathesis copolymerization of cyclic olefin monomers and comonomers, and filler materials embedded in the thermosetting materials during the metathesis copolymerization process; The comonomer is selected from norbornene derivatives or tricyclopentadiene, and the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters. The cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; The filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

2. The thermosetting composite material according to claim 1, characterized in that, The cyclic olefin monomer is selected from dicyclopentadiene.

3. The thermosetting composite material according to claim 1 or 2, characterized in that, The norbornene derivative is selected from at least one of 5-norbornene-2-methanol, 5-norbornene-2-carboxylic acid, methyl 5-norbornene-2-carboxylic acid, and 5-norbornene-2-ylacetic acid.

4. The thermosetting composite material according to claim 3, characterized in that, The molar ratio of the comonomer to the cyclic olefin monomer is 1-30:

100.

5. The thermosetting composite material according to claim 4, characterized in that, The amount of filler material added is 3%-17% of the total mass of the comonomer and the cycloolefin monomer.

6. The thermosetting composite material according to claim 1, characterized in that, The carbon fiber or glass fiber is a long fiber with a length of 70mm-90mm and a diameter of 10μm-15μm.

7. A method for preparing a thermosetting composite material, characterized in that, include: Cycloolefin monomers, comonomers, metathesis catalysts and fillers are mixed evenly. During the heating and curing process, the cycloolefin monomers and comonomers undergo metathesis copolymerization reaction under the action of the metathesis catalyst to obtain a thermosetting material. At the same time, the filler material is embedded inside the thermosetting material to obtain the thermosetting composite material. The comonomer is selected from norbornene derivatives or tricyclopentadiene, and the norbornene derivative is selected from at least one of norbornene alcohols, norbornene acids, and norbornene esters. The cyclic olefin monomer is selected from at least one of dicyclopentadiene and norbornene; The filler material is selected from at least one of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black, or silica.

8. The preparation method according to claim 7, characterized in that, The preparation of the thermosetting composite material includes: The comonomer and cyclic olefin monomer are mixed evenly, and a metathesis catalyst is added to obtain a mixture. The mixture is injected into a mold containing the filler material, and a metathesis copolymerization reaction is carried out during the heating and curing process to obtain the thermosetting composite material.

9. The preparation method according to claim 8, characterized in that, The heating and curing temperature is 80-160℃, and the heating and curing time is 30min-2h.

10. The preparation method according to any one of claims 7-9, characterized in that, The metathesis catalyst is selected from tungsten-based catalysts or ruthenium-based carbene catalysts, and the ruthenium-based carbene catalyst is a Grubbs second-generation catalyst; The amount of metathesis catalyst added is 0.1%-0.5% of the total molar amount of the comonomer and cyclic olefin monomer.

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