WO2023082310A1

WO2023082310A1 - Graphene modified conjugated diene resin and preparation method therefor and application thereof

Info

Publication number: WO2023082310A1
Application number: PCT/CN2021/131875
Authority: WO
Inventors: 李成财
Original assignee: 广东省亚克迪新材料科技有限公司
Priority date: 2021-11-09
Filing date: 2021-11-19
Publication date: 2023-05-19
Also published as: CN114031880B; CN114031880A

Abstract

A graphene modified conjugated diene resin and a preparation method therefor and an application thereof. The graphene modified conjugated diene resin comprises a conjugated diene resin and graphene, the graphene is distributed on the surface of or inside the conjugated diene resin, and the conjugated diene resin comprises at least one of a dicyclopentadiene resin and a tricyclopentadiene resin. The graphene modified conjugated diene resin has excellent corrosion resistance, the mechanical strength retention rate of the graphene modified conjugated diene resin is 85% or above by means of a severe level-5 corrosion performance test, and the mechanical strength of the graphene modified conjugated diene resin meets the use requirements of materials for automobiles, rail transit, infrastructure construction and ocean engineering. Moreover, the graphene modified conjugated diene resin is low in viscosity, has surface air-drying property, and is suitable for large-scale prepreg production.

Description

A kind of graphene modified conjugated diene resin and its preparation method and application

technical field

The invention belongs to the field of materials, and in particular relates to a graphene-modified conjugated diene resin and a preparation method and application thereof.

Background technique

The polyconjugated diene resin obtained by free radical polymerization of conjugated diene resin is a thermosetting polymer with certain toughness and rigidity, low density, water resistance and transparency, but due to the existence of active double bonds, Corrosion resistance is low. For many new energy use scenarios exposed to humidity, heat and corrosion, although conjugated diene resin has a price advantage, it is not suitable. While dicyclopentadiene is a typical product in conjugated diene resins, this problem also exists.

As a raw material with fast curing rate and low price, dicyclopentadiene has a density of only 1.08kg/m3. It has obvious cost advantages and performance advantages in mass production of polydicyclopentadiene, but its corrosion resistance is the limit It is a key factor in its application, so improving the corrosion resistance and mechanical properties of polydicyclopentadiene and improving its comprehensive performance have significant economic and social value.

Cyclopentadiene is a highly active conjugated diene, which is mainly derived from the C5 and C10 fractions in the process of petroleum cracking, and is an industrial by-product. Dicyclopentadiene has a melting point of 33.6°C and a boiling point of 170°C. It is a low-cost petroleum resin with high activity and good compatibility. It can be used for rubber modification, reducing the curing shrinkage of epoxy resin, and improving coating performance. Adhesion, enhance the wettability of the pigment, improve the leveling of the coating, etc. At present, the method for improving the chemical stability of dicyclopentadiene mainly includes catalytic hydrogenation, that is, under the conditions of a catalyst such as Ni, the process of high temperature and high pressure is adopted, and the addition and reduction reaction is carried out by _H2 and the double bond in dicyclopentadiene. Thereby improving the chemical stability of dicyclopentadiene, but the process of the addition reduction method is complicated, the yield is low, and it is not suitable for large-scale production application.

Contents of the invention

In order to overcome the above-mentioned problems in the prior art, one object of the present invention is to provide a graphene-modified conjugated diene resin.

The second object of the present invention is to provide a preparation method of graphene-modified conjugated diene resin.

The third object of the present invention is to provide the application of a graphene-modified conjugated diene resin in automobiles, rail transit, infrastructure construction, and marine engineering.

The fourth object of the present invention is to provide a graphene-modified conjugated diene resin laminate.

In order to achieve the above object, the technical scheme that the present invention takes is:

The first aspect of the present invention provides a graphene-modified conjugated diene resin, including conjugated diene resin and graphene, the graphene is distributed on the surface or inside of the conjugated diene resin, and the conjugated diene resin The resin includes at least one of dicyclopentadiene resin and tricyclopentadiene resin.

Preferably, the graphene has a sheet structure.

Graphene has chemical inertness, low polarity and excellent corrosion resistance. Adding in the conjugated diene resin in the present invention, the low polarity, small size effect and large specific surface area of graphene make graphene easy to conjugate The surface migration of the diene resin results in a high content of graphene in the surface layer of the cured product of the conjugated diene resin. At the same time, the layer stacking effect of graphene makes graphene enriched and stacked on the surface of the conjugated diene resin, forming a barrier layer resistant to salt spray corrosion, which prevents internal erosion of the material caused by water vapor penetration.

Preferably, the graphene is made of XFSG03 graphene powder; further preferably, the graphene powder has a lateral dimension of 10 μm. Graphene powder is added to the conjugated diene resin. During the curing process of the conjugated diene resin, the graphene powder will migrate into the conjugated diene resin and form a sheet-like stack in the conjugated diene resin. Thereby forming a barrier layer on the surface of the conjugated diene resin.

Preferably, the mass ratio of the graphene to the conjugated diene resin is (0.01～5):100; further preferably, the mass ratio of the graphene to the conjugated diene resin is (1～4):100; again Further preferably, the mass ratio of described graphene and conjugated diene resin is (1.5～3):100; Adopt the graphene of this ratio and conjugated diene resin, in the case of low cost, graphene modified co- Conjugated diene resin still maintains good corrosion resistance.

Preferably, the graphene-modified conjugated diene resin further includes at least one of a curing agent, a coupling agent, an internal mold release agent, a filler, and a toughening agent.

Preferably, the graphene-modified conjugated diene resin is prepared from raw materials comprising the following mass ratio: conjugated diene resin: graphene: curing agent: toughening agent: internal mold release agent: coupling agent: filler It is 100: (0.01～5): (0.8～2.5): (2～4): (0.8～1.2): (0.8～1.2): (40～60).

Preferably, the mass ratio of the conjugated diene resin: curing agent is 100: (1-2.5); further preferably, the mass ratio of the conjugated diene resin: curing agent is 100: (1-2) .

Preferably, the conjugated diene resin:toughening agent ratio is 100:(2-3.5); further preferably, the conjugated diene resin:toughening agent ratio is 100:(3-3.5).

Preferably, the conjugated diene resin: internal mold release agent ratio is 100: (0.9˜1.1); further preferably, the conjugated diene resin: internal mold release agent ratio is 100:1.

Preferably, the conjugated diene resin:coupling agent ratio is 100:(0.9˜1.1); further preferably, the conjugated diene resin:coupling agent ratio is 100:1.

Preferably, the ratio of the conjugated diene resin: filler is 100: (45-55); further preferably, the ratio of the conjugated diene resin: coupling agent is 100: (45-50).

Preferably, the dicyclopentadiene resin is DC191 resin, DC196 resin, 934 resin, 3308 resin.

Preferably, the internal release agent is at least one of stearate, fumed silicon dioxide, and vinyl silicone oil; further preferably, the stearate is selected from zinc stearate, calcium stearate , barium stearate, magnesium stearate, aluminum stearate, cadmium stearate, lead stearate at least one. The use of internal release agent makes it easier to release the mold during demoulding.

Preferably, the curing agent is TBPB free radical curing agent, BPO free radical curing agent, TBPO free radical curing agent. The curing agent and the resin particles can be cured at room temperature or under heating to obtain a cross-linked structure with a certain mechanical strength, and the cross-linked structure can confine graphene to the surface layer of the conjugated diene resin, thereby forming a barrier layer.

Preferably, the toughening agent is at least one selected from chlorinated polyethylene, chlorosulfonated polyethylene, and polychloroprene; still more preferably, the chlorinated polyethylene is CPE135A. Tougheners, such as chlorinated polyethylene, as thermoplastic materials, are added to conjugated diene resins (such as: dicyclopentadiene), heated (around 70°C) and mixed to increase the viscosity and curing of conjugated diene resins The toughness of the material facilitates the molding of graphene-modified conjugated diene resin.

Preferably, the coupling agent is at least one of KH550, KH560, and KH570. Coupling agents, such as KH550, KH560 and KH570, etc., have a trialkoxy (methoxy or ethoxy) silane group, which can be called a single-arm silane coupling agent. During the use of this silane coupling agent, the silicon-based part produces a maximum of three cross-linking points. Through cross-linking, a three-dimensional network structure is formed in the conjugated diene resin, thereby confining graphene in the three-dimensional network structure. , so that the compatibility of graphene and conjugated diene resin can be improved to avoid immiscibility.

Preferably, the filler is at least one of CaCO ₃ , Al(OH) ₃ , and MgCO ₃ . Calcium carbonate, aluminum hydroxide and other fillers can reinforce the conjugated diene resin, and further improve the mechanical strength of the graphene-modified conjugated diene resin, especially the tensile strength of the graphene-modified conjugated diene resin. strength and flexural strength.

The second aspect of the present invention provides a method for preparing the graphene-modified conjugated diene resin provided by the first aspect of the present invention, comprising the following steps: heating and mixing all raw materials to obtain the graphene-modified conjugated diene resin conjugated diene resins.

Preferably, the preparation method of the graphene-modified conjugated diene resin is specifically: mixing dicyclopentadiene resin and chlorinated polyethylene for the first time, then adding graphene, curing agent, and internal mold release agent in sequence , coupling agent and filler are mixed for the second time to obtain the graphene-modified conjugated diene resin.

Preferably, the first mixing step and/or the second mixing step is carried out by using a stirred tank.

Preferably, the mixing temperature of the first mixing step is 55°C to 85°C; more preferably, the mixing temperature of the first mixing step is 60°C to 80°C; still more preferably, the first The mixing temperature in the secondary mixing step is 65°C to 75°C.

Preferably, the mixing time of the first mixing step is 20-40 minutes; further preferably, the mixing time of the first mixing step is 25-35 minutes; the mixing time of the first mixing step is 30 minutes.

Preferably, the mixing temperature of the second mixing step is 45°C-80°C; more preferably, the mixing temperature of the second mixing step is 50°C-70°C; still more preferably, the second The mixing temperature in the secondary mixing step is 55°C to 65°C.

Preferably, the mixing time of the second mixing step is 20-40 minutes; further preferably, the mixing time of the second mixing step is 25-35 minutes; the mixing time of the second mixing step is 30 minutes.

The third aspect of the present invention provides an application of the graphene-modified conjugated diene resin provided in the first aspect of the present invention in automobiles, rail transit, infrastructure construction, and ocean engineering.

The fourth aspect of the present invention provides a graphene-modified conjugated diene resin laminate, including the graphene-modified conjugated diene resin provided by the first aspect of the present invention.

Preferably, the graphene-modified conjugated diene resin laminate further includes glass fibers.

Preferably, the mass percentage of the graphene-modified conjugated diene resin is 31%-47%.

Preferably, the graphene-modified conjugated diene resin laminate is prepared by the following preparation method. The graphene-modified conjugated diene resin is mixed with glass fibers and hot-pressed.

Preferably, the hot pressing temperature used in the hot pressing forming step is 100°C to 150°C; further preferably, the hot pressing temperature used in the hot pressing forming step is 110°C to 140°C; still more preferably, The hot pressing temperature adopted in the hot pressing forming step is 110°C-130°C.

Preferably, the hot pressing time used in the hot pressing forming step is 20 to 40 minutes; further preferably, the hot pressing time used in the hot pressing forming step is 25 to 35 minutes; still more preferably, the hot pressing The hot pressing time adopted in the forming step is 30min.

Preferably, the glass fibers have an areal density of 400 gsm.

Preferably, the graphene-modified conjugated diene resin laminate is at least one of laminates for offshore power generation platforms, laminates for ocean floating islands, and laminates for offshore oil drilling platforms.

The graphene-modified conjugated diene resin laminate in the present invention can be used for a long time in a marine environment with high salt spray, and overcomes the problems of short service life and easy corrosion and failure of unsaturated conjugated diene resin in a marine environment. It has broad application prospects and application value on offshore power generation platforms, ocean floating islands and offshore oil drilling platforms.

The beneficial effects of the present invention are: the graphene-modified conjugated diene resin of the present invention has excellent corrosion resistance, and after passing the corrosion performance test of the severe level 5, its mechanical strength retention rate is above 85%, and its mechanical strength meets the requirements of automobiles. , rail transit, infrastructure, ocean engineering materials use requirements. At the same time, the graphene-modified conjugated diene resin in the invention has low viscosity, has surface air-drying properties, and is suitable for large-scale prepreg production.

The preparation method in the present invention adds graphene into the conjugated diene resin through physical blending, the preparation method is simple and easy to operate, the raw material price is low, the source is abundant, and it is suitable for mass promotion and application.

Description of drawings

Fig. 1 is the SEM figure of the dicyclopentadiene resin of graphene modification in embodiment 1;

Fig. 2 is the tensile strength performance figure of laminated board in comparative example 1 after salt spray corrosion;

Fig. 3 is the tensile strength performance figure of laminated board in embodiment 1 after salt spray corrosion;

Fig. 4 is the tensile strength performance figure of laminated board in embodiment 2 after salt spray corrosion;

Fig. 5 is the flexural strength performance figure of laminated board in comparative example 1 after salt spray corrosion;

Fig. 6 is the performance figure of flexural strength of laminated board in embodiment 1 after salt spray corrosion;

Fig. 7 is the flexural strength performance figure of laminated board in embodiment 2 after salt spray corrosion;

Fig. 8 is the structure of the dicyclopentadiene resin modified by graphene in embodiment 1.

Detailed ways

The specific implementation of the present invention will be described in further detail below in conjunction with the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be pointed out that, if there are any processes in the following that are not specifically described in detail, those skilled in the art can realize or understand with reference to the prior art. The reagents or instruments used were not indicated by the manufacturer, and they were regarded as conventional products that can be purchased from the market.

Example 1

The graphene-modified dicyclopentadiene resin in this example is made from components comprising the following parts by weight: 100 parts of dicyclopentadiene resin, 3 parts of chlorinated polyethylene, 2 parts of graphene, 1 part of gas phase SiO ₂ , 5 parts of MgO, 45 parts of Al(OH) ₃ , 1 part of zinc stearate, 1 part of KH570, 0.5 parts of vinyl silicone oil and 1.5 parts of TBPB free radical curing agent.

The graphene-modified dicyclopentadiene resin in this example is prepared according to the following preparation method, comprising the following steps:

Stir and mix 100 parts of dicyclopentadiene resin and 3 parts of chlorinated polyethylene at 70°C for 30 minutes, then add 2 parts of graphene, 1 part of gas-phase SiO ₂ , 5 parts of MgO, and 45 parts of Al(OH) _{3 at 60} °C , 1 part of zinc stearate, 1 part of KH570, 0.5 part of vinyl silicone oil and 1.5 parts of TBPB (tert-butyl perbenzoate) free radical curing agent, mixed for 20 min to obtain the graphene-modified dicyclopentadiene in this example Vinyl resin.

Test the SEM image of the graphene-modified dicyclopentadiene resin prepared in this example, specifically see Figure 1, as can be seen, graphene in Figure 1 is distributed on the surface of the dicyclopentadiene resin in a stacked form.

The present invention adds graphene into the dicyclopentadiene resin through physical blending, and the graphene is easy to migrate to the material surface in the dicyclopentadiene resin due to its low polarity, small size effect, high specific strength and large specific surface area. At the same time, during the high-temperature curing process of dicyclopentadiene resin, the viscosity of the resin decreases, which reduces the migration energy barrier of graphene. Finally, with the curing of dicyclopentadiene resin, graphene stacks rich in carbon dioxide are formed on the surface of dicyclopentadiene resin. set of barrier layers. In addition, the formation of cross-linked structure after curing of dicyclopentadiene resin has a stabilizing effect on the enrichment of surface graphene, forming the structure of dicyclopentadiene resin and graphene as shown in Figure 8. The surface layer of the dicyclopentadiene resin cured product has a high graphene content, and the layer stacking effect of the graphene has a barrier effect on the water vapor with a high corrosion content, preventing the erosion inside the material.

Example 2

The graphene-modified dicyclopentadiene resin in this example is made by the components comprising the following parts by weight: 100 parts of dicyclopentadiene resin, 3 parts of chlorinated polyethylene, 4 parts of graphene, 1 part of gas phase SiO ₂ , 5 parts of MgO, 45 parts of Al(OH) ₃ , 1 part of zinc stearate, 1 part of KH570, 0.5 parts of vinyl silicone oil and 1.5 parts of TBPB free radical curing agent.

Stir and mix 100 parts of dicyclopentadiene resin and 3 parts of chlorinated polyethylene at 70°C for 30 minutes, then add 4 parts of graphene, 1 part of gas phase SiO ₂ , 1 part of KH570, 5 parts of MgO, and 45 parts of Al at 60°C (OH) ₃ , 1 part of zinc stearate, 0.5 part of vinyl silicone oil and 1.5 parts of TBPB (tert-butyl perbenzoate) free radical curing agent, mixed 20min to obtain the graphene-modified dicyclopentadiene in this example Vinyl resin.

Comparative example 1

Compared with Example 1, this example differs in that: this example does not contain graphene, and the dicyclopentadiene resin in this example is prepared according to the preparation method in Example 1.

Performance Testing:

The resins prepared in Example 1, Example 2, and Comparative Example 1 were mixed with glass fiber plain cloth with an area density of 400 gsm (g/cm ² ) to prepare prepregs, and then cured at 120°C for 30 minutes by molding Obtain the dicyclopentadiene resin laminated board of solid content 39%, with sample preparation machine, dicyclopentadiene resin laminated board is made into dumbbell-shaped tensile sample and bending sample, then test respectively the laminated board made by embodiment 1 1. Tensile strength, flexural strength and corrosion resistance of the laminate made in Example 2 and the laminate made in Comparative Example 1. Wherein, the flexural strength and tensile strength are tested in Example 1, Example 2 and Comparative Example 1 according to the methods recorded in ASTM D7264 and ASTM D3039, and the tensile strength and flexural strength results obtained by the test are recorded in Table 1 below.

Then, the dumbbell-shaped dicyclopentadiene resin laminates prepared in Example 1, Example 2 and Comparative Example 1 were subjected to a salt spray corrosion test, and the specific test results are shown in FIGS. 2 to 7 . The tensile strength of the laminate prepared in Comparative Example 1 after salt spray corrosion is shown in FIG. 2 , and the flexural strength is shown in FIG. 5 . Among them, curves (b), curves (a), curves (c), curves (e) and curves (d) in Figure 2 are laminated boards in the absence of, 1 time, 2 times, 3 times and 3 times, respectively. Tensile strength curves of 4 salt spray test cycles; curve (b), curve (a), curve (c), curve (d) and curve (e) in Figure 5 are laminated boards without and once , carry out 2 times, carry out 3 times, carry out the flexural strength curve of 4 salt spray test cycles; The tensile strength of the laminate made by embodiment 1 after salt spray corrosion is shown in Figure 3, and the flexural strength is shown in Figure 6 shown. Among them, curves (b), curves (a), curves (e), curves (d) and curves (c) in Fig. 3 are laminated boards that are not processed, 1 time, 2 times, 3 times, 4 times Tensile strength curve during the second salt spray test cycle; curve (a), curve (c), curve (b), curve (d) and curve (e) in Figure 6 are laminates without, once, once, Bending strength curves when the salt spray test is performed 2 times, 3 times, and 4 times. The tensile strength of the laminate prepared in Example 2 after salt spray corrosion is shown in FIG. 4 , and the bending strength is shown in FIG. 7 . Among them, the curve (a), curve (b), curve (d), curve (e) and curve (c) in Figure 4 are laminated boards that are not processed, 1 time, 2 times, 3 times, 4 times Tensile strength curve during salt spray test; Curve (a), curve (b), curve (c), curve (d) and curve (e) in Fig. Bending strength curves when salt spray tests were performed 2 times, 3 times, and 4 times.

The salt spray corrosion test method and conditions are:

The salt spray corrosion test is carried out according to the GB/T 2423.18-2012 standard. The salt spray treatment conditions are: the solution used is 5% NaCl solution, the salt spray settlement: 1-2mL/80cm ² /h, and the treatment time is 2h. The humidity and heat storage conditions are: the temperature of the test chamber is 40°C, the humidity is 93% RH, and the test time is 22 hours. The above salt spray treatment and humidity and heat storage are repeated four times, and the total treatment time is 4 days. After the test, place it at 23°C ± 2°C, 45%RH-55%RH (RH is relative humidity) for 72h, the total test duration is 7 days, complete a cycle of salt spray corrosion test, take out test example 1, implement The tensile and bending properties of the dumbbell-shaped dicyclopentadiene resin laminates prepared in Example 2 and Comparative Example 1 are recorded in Table 1 below. Carry out the salt spray corrosion test of the second cycle to the laminated boards made in embodiment 1, embodiment 2 and comparative example 1 through one cycle of salt spray corrosion test, then take out the test tensile and bending properties, test result record In Table 1 below. The dumbbell-shaped dicyclopentadiene resin laminates made in the embodiment 1, embodiment 2 and comparative example 1 of the salt spray corrosion test of two cycles are carried out to the salt spray corrosion test of the third cycle, then take out the test Tensile and flexural properties, the test results are reported in Table 1 below. The dumbbell-shaped dicyclopentadiene resin laminates made in the embodiment 1, embodiment 2 and comparative example 1 of the salt spray corrosion test of three cycles are carried out to the salt spray corrosion test of the fourth cycle, then take out the test Tensile and flexural properties, the test results are reported in Table 1 below. The total test duration of the four cycles of the salt spray corrosion test is 28 days, reaching the severity level (5). At the same time, the corrosion resistance of dicyclopentadiene resin is characterized by tensile and bending performance attenuation. The specific results are shown in Table 1 below:

Table 1 Bending strength and tensile strength test results

It can be seen from Table 1 that after one salt spray corrosion test cycle, the tensile strength of the dicyclopentadiene laminate without graphene in Comparative Example 1 decreased by 8.25%, and the bending strength decreased by 3.49%. In Example 1, the modified dicyclopentadiene laminate with 2 parts of graphene was added, the tensile strength decreased by 4.06%, and the bending strength decreased by 2.87%. Add the modified dicyclopentadiene laminate of 4 parts of graphene in embodiment 2, tensile strength descends 3.77%, flexural strength descends 1.86%, this shows that the adding of sheet graphene has improved the resistance of dicyclopentadiene laminate corrosion performance.

After two salt spray corrosion test cycles, the tensile strength of the dicyclopentadiene laminate without graphene in Comparative Example 1 decreased by 16.90%, and the bending strength decreased by 9.61%. In Example 1, 2 parts of graphene were added to the dicyclopentadiene laminate, the tensile strength decreased by 8.20%, and the bending strength decreased by 5.99%. In Example 2, the dicyclopentadiene laminate with 4 parts of graphene was added, the tensile strength decreased by 6.92%, and the bending strength decreased by 4.14%.

After three salt spray corrosion test cycles, the tensile strength of the dicyclopentadiene laminate without graphene in Comparative Example 1 decreased by 27.81%, and the bending strength decreased by 18.23%. Add 2 parts of graphene dicyclopentadiene laminates in Example 1, the tensile strength drops by 11.00%, and the bending strength drops by 10.43%. Add 4 parts of graphene dicyclopentadiene laminates in Example 2, the tensile strength drops by 9.13%, and the bending strength drops by 6.89%.

After 4 salt spray corrosion test cycles, the tensile strength of the dicyclopentadiene laminate without graphene in Comparative Example 1 decreased by 36.91%, and the bending strength decreased by 28.71%. In Example 1, the dicyclopentadiene laminate with 2 parts of graphene was added, the tensile strength decreased by 14.96%, and the bending strength decreased by 14.85%. Add 4 parts of graphene dicyclopentadiene laminates in Example 2, the tensile strength drops by 11.69%, and the bending strength drops by 9.32%.

From the above analysis, it can be seen that as the corrosion time prolongs, the decline in the mechanical properties of the dicyclopentadiene laminate prepreg in Comparative Example 1 gradually increases. This is because the inner layer of the material is corroded and wick diffusion occurs. effect, resulting in increased corrosion of the material. The decline in the mechanical properties of the dicyclopentadiene laminate in Example 1 and Example 2 after adding graphene tends to slow down, because the modification of graphene has an insulating effect on the surface of the dicyclopentadiene laminate, blocking The corrosion of the inner layer of the material by the corrosive components is eliminated, and the decline in mechanical properties is significantly lower than that of the dicyclopentadiene laminate without graphene. When the amount of graphene added increases from 2 parts to 4 parts, the performance retention rate has a certain improvement, but the improvement rate is low.

The embodiments of the present invention have been described in detail above, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those of ordinary skill in the art without departing from the gist of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict.

Claims

A graphene-modified conjugated diene resin, characterized in that: it includes a conjugated diene resin and graphene, the graphene is distributed on the surface or inside of the conjugated diene resin, and the conjugated diene resin includes a bicyclic At least one of pentadiene resin and tricyclopentadiene resin.
The graphene-modified conjugated diene resin according to claim 1, characterized in that: the graphene has a lamellar structure.
The graphene-modified conjugated diene resin according to claim 1 or 2, characterized in that: the mass ratio of the graphene to the conjugated diene resin is (0.01-5):100.
Graphene-modified conjugated diene resin according to claim 1, is characterized in that: described graphene-modified conjugated diene resin also comprises curing agent, coupling agent, internal release agent, filler, toughening at least one of the agents.
The graphene-modified conjugated diene resin according to claim 4, wherein: the graphene-modified conjugated diene resin is made from raw materials comprising the following mass ratio: conjugated diene resin: graphene : Curing agent: Toughener: Internal release agent: Coupling agent: Filler is 100: (0.01～5): (0.8～2.5): (2～4): (0.8～1.2): (0.8～1.2) : (40~60).
The graphene-modified conjugated diene resin according to claim 4 or 5, characterized in that: the internal mold release agent is at least one of stearate, fumed silica, and vinyl silicone oil.
The graphene-modified conjugated diene resin according to claim 4 or 5, characterized in that: the toughening agent is at least one of chlorinated polyethylene, chlorosulfonated polyethylene, and polychloroprene .
The graphene-modified conjugated diene resin according to claim 4 or 5, characterized in that: the curing agent is a TBPB radical curing agent.
The preparation method of the graphene-modified conjugated diene resin according to any one of claims 4 to 8, characterized in that: comprising the following steps: heating and mixing all raw materials to obtain the graphene-modified conjugated diene resin diene resins.
The application of the graphene-modified conjugated diene resin described in any one of claims 1 to 8 in automobiles, rail transit, infrastructure construction, and ocean engineering.