A method of manufacturing a pdcpd resin-glass fiber composite

Abstract

The application provides a manufacturing method of a PDCPD resin-glass fiber composite material, which is made of a certain amount of DCPD raw material, glass fiber and various types of additives; wherein the DCPD raw material is composed of 90-95 parts of DCPD and 5-10 parts of TCPD, the glass fiber is glass fiber untwisted roving cloth, and the curing agent is composed of 3-9 parts of Grubbs second-generation catalyst, 90-95 parts of solvent and 0.4-0.6 parts of polymerization inhibitor and is used for controlling the forming speed of the composite material. Meanwhile, the glass fiber is added into the composite material system, so that the composite material has excellent mechanical properties, and the application of the polydicyclopentadiene composite material is expanded.

Description

Technical Field

[0001] This invention relates to the field of resin materials technology, and in particular to a thermosetting resin, a glass fiber composite material, its preparation method and application. Background Technology

[0002] Thermosetting resins are important polymer materials with excellent properties in terms of chemical resistance, mechanical strength, and electrical insulation. Under certain controlled conditions, the molecular structure of thermosetting resins undergoes an irreversible chemical cross-linking reaction, resulting in a highly cross-linked network structure with excellent dimensional stability after curing. This stable characteristic makes them widely used in electronics manufacturing, construction, automotive, and aerospace industries. Currently, epoxy resins are the most commonly used thermosetting resins on the market. However, epoxy resins still have shortcomings in terms of curing time and mechanical properties. To meet the rapidly evolving application requirements of various fields, it is necessary to develop a material with short curing time, low reaction energy consumption, and excellent mechanical properties.

[0003] Electric vehicle battery packs are located under the floor. To improve the collision resistance of these batteries, OEMs currently increase the thickness of the bottom protection plate to achieve a "crash-resistant" effect. However, this approach leads to a significant increase in vehicle weight, affecting core parameters of electric vehicles that consumers care about, such as driving range. Fiber-reinforced PDCPD resin composite materials offer excellent impact resistance and have broad application prospects. They can significantly improve the bottom protection capabilities of new energy vehicles, resulting in lighter and safer protective plates.

[0004] Currently, the fibers used in composite materials are mainly carbon fiber or glass fiber. Due to the poor compatibility between the sizing agent on the surface and PDCPD, the bonding degree between PDCPD resin and fiber is insufficient, and the effect of 1+1>2 cannot be achieved.

[0005] CN112961279A describes adding TCPD to DCPD to improve the rigidity of PDCPD. Because tricyclopentadiene TCPD has a larger molecular weight than dicyclopentadiene DCPD, it exhibits greater rigidity. The rigidity of the copolymer of polytricyclopentadiene PTCPD and polydicyclopentadiene PDCPD is greater than that of existing polydicyclopentadiene polymers. While TCPD can improve the rigidity of DCPD, PTCPD itself is non-polar, directly leading to inherently weak bonding between it and fibers or fiber fabrics when applied to fiber composites. For example, CN112980130A discloses a polytricyclopentadiene PTCPD fiber composite material preparation process that requires complex and precise modification of the fiber surface, increasing the complexity and cost of the preparation. Summary of the Invention

[0006] This invention provides a thermosetting resin, a glass fiber composite material, a preparation method thereof, and its application. The thermosetting resin provided by this invention has high mechanical properties and a short curing time. The glass fiber composite material prepared by combining the thermosetting resin of this invention with glass fiber has the characteristics of light weight, high strength, and corrosion resistance, which can meet the requirements of protective plates for new energy vehicles and achieve lightweighting of protective plates for new energy vehicles while ensuring strength and safety.

[0007] In a first aspect, the present invention provides a PDCPD thermosetting resin, wherein the thermosetting resin is obtained by polymerization reaction of a dicyclopentadiene system, a curing agent, and an additive, wherein the mass ratio of the dicyclopentadiene system, the curing agent, and the additive is (10-50):(0.5-3):(0.001-0.03); the dicyclopentadiene system comprises tricyclopentadiene and dicyclopentadiene in a mass ratio of 5:95; the curing agent comprises a Grubbs second-generation catalyst and a solvent in a mass ratio of (0.5-2):(50-90), wherein the solvent is selected from any one or a combination of at least two of cyclohexylbenzene, a silane coupling agent, and dichloromethane, preferably a silane coupling agent; the additive is selected from any one or a combination of at least two of triphenylphosphine, tributyl phosphite, and 2,4,6-tris(dimethylaminomethyl)phenol, preferably tributyl phosphite.

[0008] As a preferred embodiment of the present invention, the mass ratio of Grubbs second-generation catalyst to solvent in the curing agent is 1:83.3.

[0009] The thermosetting resin provided by this invention has high toughness and high strength. The polymerization reaction takes 3 to 5 minutes, and the resulting polymer has high toughness, excellent coating performance, and the surface can be directly painted.

[0010] When the mass ratio of the dicyclopentadiene raw material, curing agent, and additive is within the range of this invention, a resin material with high modulus, high impact strength, and high creep resistance can be obtained. When the amount of curing agent is too large, the reaction process will produce a burst polymerization phenomenon. When the amount of additive is too small, the reaction rate is too fast, making it difficult to enter the mold for molding.

[0011] According to the thermosetting resin of the present invention, the silane coupling agent is selected from any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, ethyl silicate, and γ-aminopropyltriethoxysilane, preferably vinyltriethoxysilane.

[0012] According to the thermosetting resin of the present invention, the preparation method of the dicyclopentadiene system is as follows: heating dicyclopentadiene to 180-220°C and holding for 2-4 hours to obtain a mixture of dicyclopentadiene and tricyclopentadiene, and adding new dicyclopentadiene to the mixture so that the mass ratio of tricyclopentadiene to dicyclopentadiene in the dicyclopentadiene system is 5:95.

[0013] In the preparation method of the dicyclopentadiene system, the self-polymerization reaction of dicyclopentadiene is as follows:

[0014]

[0015] The curing reaction of dicyclopentadiene is shown below:

[0016]

[0017] In a second aspect, the present invention provides a PDCPD resin-glass fiber composite material, the composite material comprising the thermosetting resin and glass fiber described in the first aspect, wherein the glass fiber is the reinforcing phase and the thermosetting resin is the matrix.

[0018] According to the composite material of the present invention, the glass fiber is selected from any one or a combination of at least two of glass fiber roving, alkali-free glass fiber emulsion chopped strand mat, and alkali-free glass fiber powder chopped strand mat.

[0019] According to the composite material of the present invention, the content of the thermosetting resin is 30-40% and the content of the glass fiber is 60-70% based on the total mass of the composite material (100%).

[0020] The composite material obtained by this invention has the characteristics of being lightweight, high-strength, and corrosion-resistant.

[0021] Thirdly, the present invention provides a method for preparing the composite material described in the second aspect, the method comprising the following steps: mixing a dicyclopentadiene system, a curing agent and an additive to obtain a mixed adhesive solution of a resin composition; impregnating glass fibers in the mixed adhesive solution using a vacuum infusion molding method; placing the mixture in an oven; and curing to obtain the composite material.

[0022] The curing conditions for the curing molding are as follows: first, at 50-90℃ for 3-5 minutes, preferably at 60℃ for 5 minutes, and then at 140℃ for 0.5-1 hour, preferably 1 hour.

[0023] Fourthly, the present invention provides a battery protection plate, which is made of the composite material described in the second aspect.

[0024] The battery protection plate provided by this invention has excellent mechanical properties and achieves lightweight design.

[0025] The PDCPD resin-glass fiber described in this invention has the following advantages compared with existing materials:

[0026] Polydicyclopentadiene has a lower density, ranging from 0.5 to 1.5 g / cm³. 3 Therefore, its composite material products have a more obvious lightweight effect. At the same time, polydicyclopentadiene has the characteristics of high modulus, high impact strength and high creep resistance. Compared with the battery protection plate materials commonly used on the market, it can not only further realize the lightweighting of automobiles, but also further improve the comprehensive performance of automobile materials.

[0027] Compared to commonly used resin monomers (such as epoxy resin), the monomer dicyclopentadiene has a very low viscosity (0.3 Pa·s), a faster curing reaction rate, a lower reaction temperature, and a convenient adjustment of polymerization time, making it more energy-efficient in material molding processes and a more environmentally friendly green polymer engineering plastic. Detailed Implementation

[0028] To further understand the above-mentioned objectives, features and advantages of the present invention, the present invention will be described below by way of examples, wherein the embodiments described in the specification are only some embodiments of the present invention, and not all embodiments.

[0029] The raw materials used in the embodiments of this invention are shown in Table 1:

[0030] serial number name factory 1 Dicyclopentadiene Beijing Bailingwei Technology Co., Ltd. 2 Alkali-free glass fiber emulsion chopped strand mat (450gsm) Chinese Giant Stone 3 Alkali-free glass fiber powder chopped strand mat (450gsm) Chinese Giant Stone 4 Untwisted fiberglass roving (400gsm, plain weave) Chinese Giant Stone 5 Grubbs second-generation catalyst Aladdin 6 Cyclohexylbenzene Aladdin 7 Silane coupling agents Aladdin 8 Tributyl phosphite Aladdin 9 Triphenylphosphine Aladdin

[0031] Preparation Example 1

[0032] This preparation example provides a dicyclopentadiene raw material and its preparation method, the preparation method comprising the following steps:

[0033] 3L of dicyclopentadiene was placed in a three-necked flask, heated to 180°C, and allowed to undergo a self-polymerization reaction. After reflux for 4 hours, dicyclopentadiene containing trimeropeptadiene was obtained. The content of trimeropeptadiene was determined by gas chromatography.

[0034] The dicyclopentadiene containing tricyclopentadiene obtained above was mixed with pure dicyclopentadiene to prepare a mass ratio of tricyclopentadiene to dicyclopentadiene of 5:95, thus obtaining the dicyclopentadiene raw material of the present invention.

[0035] Example 1-1

[0036] This embodiment provides a method for preparing PDCPD resin-glass fiber composite material, the preparation method including the following steps:

[0037] Dissolve 95 mg of Grubbs catalyst in 5 ml of cyclohexylbenzene, add 0.006 g of tributyl phosphite, mix well, and then add to 140 g of dicyclopentadiene raw material. Stir, evacuate and purge with nitrogen three times in a row, and then pour into a mold through vacuum injection, with 5 layers of glass fiber untwisted roving.

[0038] After the glass fiber is completely impregnated, place the mold in a 60°C oven and keep it for 5 minutes, then raise the temperature to 140°C and keep it for 1 hour.

[0039] After complete cooling, the mold is opened to obtain the composite material.

[0040] Examples 1-2

[0041] This embodiment provides a method for preparing a glass fiber composite material, which is the same as that in Embodiment 1-1, except that the glass fiber used is alkali-free glass fiber emulsion chopped strand mat.

[0042] Examples 1-3

[0043] This embodiment provides a method for preparing a glass fiber composite material, which is the same as that in Embodiment 1-1, except that the glass fiber used is alkali-free glass fiber powder chopped strand mat.

[0044] Examples 1-4

[0045] This embodiment provides a method for preparing glass fiber composite material, which is the same as that in Embodiment 1-1, except that the catalyst solvent used is a silane coupling agent.

[0046] Examples 1-5

[0047] This embodiment provides a method for preparing a glass fiber composite material, which is the same as that in Example 1-1, except that the additive used is triphenylphosphine.

[0048] Comparative Example 1-1

[0049] This embodiment provides a method for preparing a glass fiber composite material, which is the same as that in Embodiments 1-1, except that the matrix resin is epoxy resin, and the ratio of epoxy resin to the corresponding catalyst and additives is 45:20:1.

[0050] Performance testing

[0051] The performance of the glass fiber composite materials obtained in the above embodiments and comparative examples was tested:

[0052] Tensile properties: Tested according to GB / T 13096-2008.

[0053] Bending performance: Tested according to GB / T 13096-2008.

[0054] Impact strength: Tested according to GB / T 2918-1998.

[0055] The test results are shown in Table 2:

[0056] project Tensile strength / MPa Tensile modulus / Gpa Elongation at break / % Bending strength / MPa Flexural modulus / Gpa Example 1-1 687.7 42.06 5.13 592.86 15.54 Examples 1-2 543.77 36.47 4.91 419.69 10.73 Examples 1-3 562.54 32.79 5.23 558.12 14.5 Examples 1-4 671.59 42.62 6.11 576.32 16.84 Examples 1-5 670.62 41.47 5.89 582.49 15.18 Comparative Example 1-1 650.36 36.1 2.1 203 12.5

[0057] As shown in Table 2, the glass fiber composite material prepared by the method of the present invention has a tensile strength of 500-700 MPa, a tensile modulus of 35-45 GPa, a flexural strength of 400-600 MPa, a flexural modulus of up to 10 GPa, and an elongation at break of 4-7%. Compared with conventional glass fiber composite materials, it has higher strength and better toughness, while having similar impact strength, which can meet the requirements of hydrogen storage cylinder frames. A comparison of Examples 1-1, 1-2, and 1-3 shows that for dicyclopentadiene resin, the composite material obtained by using untwisted roving as glass fiber exhibits superior performance. A comparison of Examples 1-1 and 1-4 shows that the composite material obtained by using cyclohexylbenzene as the catalyst solvent has slightly higher tensile and flexural strength, but slightly lower elongation at break. A comparison of Examples 1-1 and 1-5 shows that the performance of the composite material is not significantly different regardless of whether tributyl phosphite or triphenylphosphine is used as the additive. A comparison of Examples 1-1 and Comparative Example 1-1 shows that when other types of resin are used, the elongation at break of the obtained composite material is reduced by half, indicating that the composite material prepared using the method of this invention has better toughness.

Claims

1. A PDCPD thermosetting resin, characterized in that, The thermosetting resin is obtained by polymerization of a dicyclopentadiene system, a curing agent, and additives, wherein the mass ratio of the dicyclopentadiene system, curing agent, and additives is (10-50):(0.5-3):(0.001-0.03); the dicyclopentadiene system includes tricyclopentadiene and dicyclopentadiene in a mass ratio of 5:95; the curing agent includes Grubbs second-generation catalyst and solvent in a mass ratio of (0.5-2):(50-90), wherein the solvent is selected from any one or at least two combinations of cyclohexylbenzene, silane coupling agent, and dichloromethane; the additives are selected from any one or at least two combinations of triphenylphosphine, tributyl phosphite, and 2,4,6-tris(dimethylaminomethyl)phenol.

2. The thermosetting resin according to claim 1, characterized in that, The silane coupling agent is selected from any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(β-methoxyethoxy)silane, ethyl silicate, and γ-aminopropyltriethoxysilane.

3. The thermosetting resin according to claim 1, characterized in that... The preparation method of the dicyclopentadiene system is as follows: Dicyclopentadiene is heated to 180-220℃ and kept at that temperature for 2-4 hours to obtain a mixture of dicyclopentadiene and tricyclopentadiene. New dicyclopentadiene is added to the mixture so that the mass ratio of tricyclopentadiene to dicyclopentadiene in the dicyclopentadiene system is 5:

95.

4. A PDCPD resin-glass fiber composite material, characterized in that, The composite material comprises the thermosetting resin and glass fiber as described in any one of claims 1-3, wherein the glass fiber is the reinforcing phase and the thermosetting resin is the matrix.

5. The composite material according to claim 4, characterized in that, The glass fiber is selected from any one or a combination of at least two of the following: untwisted glass fiber roving, alkali-free glass fiber emulsion chopped strand mat, and alkali-free glass fiber powder chopped strand mat.

6. The composite material according to claim 4, characterized in that, Based on the total mass of the composite material as 100%, the content of the thermosetting resin is 30-40%, and the content of the glass fiber is 60-70%.

7. The method for preparing the composite material according to claim 4, characterized in that, The method includes the following steps: mixing a dicyclopentadiene system, a curing agent, and additives to obtain a mixed resin composition; impregnating glass fibers in the mixed resin composition using a vacuum casting molding method; placing the mixture in an oven; and curing to obtain the composite material.

8. The method according to claim 7, characterized in that, The curing conditions for the curing process are as follows: first, at 50-90℃ for 3-5 minutes, followed by post-treatment at 140℃ for 0.5-1 hour.

9. The method according to claim 7, characterized in that, The curing conditions for the curing process are: first, 5 minutes at 60°C, followed by 1 hour of post-treatment at 140°C.

10. A battery protection plate, characterized in that, The battery protective plate is made of the composite material described in any one of claims 4-6.

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