CN114031880B - Graphene modified conjugated diene resin and preparation method and application thereof - Google Patents
Graphene modified conjugated diene resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene modified conjugated diene resin, a preparation method and application thereof, wherein the graphene modified conjugated diene resin comprises conjugated diene resin and graphene, the graphene is distributed on the surface or inside of the conjugated diene resin, and the conjugated diene resin comprises at least one of dicyclopentadiene resin and tricyclopentadiene resin. The graphene modified conjugated diene resin has excellent corrosion resistance, and the mechanical strength retention rate is above 85% after the severe grade 5 corrosion performance test, so that the mechanical strength meets the use requirements of materials for automobiles, rail transit, infrastructure and ocean engineering. Meanwhile, the graphene modified conjugated diene resin disclosed by the invention is low in viscosity, has surface air-drying property and is suitable for large-scale prepreg production.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to graphene modified conjugated diene resin, and a preparation method and application thereof.
Background
The conjugated diene resin is a thermosetting polymer with certain toughness and rigidity, has low density, water resistance and transparency, but has low corrosion resistance due to the existence of active double bonds, and is not applicable to a plurality of new energy use scenes exposed to damp heat and corrosion although having price advantage. The same problem is also present when dicyclopentadiene is a typical product of conjugated diene resins.
The dicyclopentadiene is used as a raw material with high curing rate and low price, the density is only 1.08kg/m < 3 >, and the dicyclopentadiene has obvious cost advantage and performance advantage in mass production, but the corrosion resistance is a key factor for limiting the application of the dicyclopentadiene, so that the dicyclopentadiene has obvious economic value and social value by improving the corrosion resistance and mechanical property of the dicyclopentadiene and improving the comprehensive use performance of the dicyclopentadiene.
Cyclopentadiene is a high-activity conjugated diene, mainly derived from C5 and C10 fractions in petroleum cracking process, and belongs to industrial byproducts. Dicyclopentadiene has a melting point of 33.6 ℃ and a boiling point of 170 ℃, is a low-cost petroleum resin, has high activity and good compatibility, can be used for modifying rubber, reduces the curing shrinkage of epoxy resin, improves the adhesiveness of paint, enhances the wettability of pigment and improves the paintLeveling of the film, and the like. The prior method for improving the chemical stability of dicyclopentadiene mainly comprises a catalytic hydrogenation method, namely, under the condition of Ni and other catalysts, adopting a high-temperature and high-pressure process to pass H 2 And the double bond in dicyclopentadiene is subjected to addition reduction reaction, so that the chemical stability of dicyclopentadiene is improved, but the addition reduction method is complex in process, low in yield and not suitable for large-scale production and application.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide a graphene modified conjugated diene resin.
The second object of the invention is to provide a preparation method of the graphene modified conjugated diene resin.
The invention further aims to provide application of the graphene modified conjugated diene resin in automobiles, rail transit, infrastructure and ocean engineering.
The fourth object of the invention is to provide a graphene modified conjugated diene resin laminate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a graphene modified conjugated diene resin, which comprises conjugated diene resin and graphene, wherein the graphene is distributed on the surface or inside of the conjugated diene resin, and the conjugated diene resin comprises at least one of dicyclopentadiene resin and tricyclopentadiene resin.
Preferably, the graphene is a lamellar structure.
The graphene has the characteristics of chemical inertness, low polarity and excellent corrosion resistance, and the low polarity, small size effect and large specific surface area of the graphene are added into the conjugated diene resin, so that the graphene is easy to migrate to the surface of the conjugated diene resin, and the surface graphene content of the conjugated diene resin cured product is high. Meanwhile, due to the lamellar stacking effect of the graphene, the graphene is enriched and stacked on the surface of the conjugated diene resin, so that a salt mist corrosion resistant barrier layer is formed, and the internal erosion of the material caused by water vapor permeation is prevented.
Preferably, the graphene adopts graphene powder with XFSG03 as a raw material; further preferably, the lateral dimension of the graphene powder is 10 μm. The graphene powder is added into the conjugated diene resin, and the graphene powder migrates into the conjugated diene resin in the curing process of the conjugated diene resin and forms a flaky stack in the conjugated diene resin, so that a barrier layer is formed 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; still more preferably, the mass ratio of the graphene to the conjugated diene resin is (1.5-3) 100; the graphene modified conjugated diene resin still maintains good corrosion resistance under the condition of low cost by adopting the graphene and the conjugated diene resin in the proportion.
Preferably, the graphene modified conjugated diene resin further comprises 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 the following raw materials in mass ratio: conjugated diene resin: graphene: curing agent: toughening agent: and (3) an internal mold release agent: coupling agent: the filler is 100: (0.01-5): (0.8-2.5): (2-4): (0.8-1.2): (0.8-1.2): (40-60).
Preferably, the conjugated diene resin: the mass ratio of the curing agent is 100: (1-2.5); further preferably, the conjugated diene resin: the mass ratio of the curing agent is 100: (1-2).
Preferably, the conjugated diene resin: the toughening agent is 100: (2-3.5); further preferably, the conjugated diene resin: the toughening agent is 100: (3-3.5).
Preferably, the conjugated diene resin: the internal mold release agent is 100: (0.9 to 1.1); further preferably, the conjugated diene resin: the internal mold release agent is 100:1.
preferably, the conjugated diene resin: the coupling agent is 100: (0.9 to 1.1); further preferably, the conjugated diene resin: the coupling agent is 100:1.
preferably, the conjugated diene resin: the filler is 100: (45-55); further preferably, the conjugated diene resin: the coupling agent is 100: (45-50).
Preferably, the dicyclopentadiene resin is a DC191 resin, a DC196 resin, a 934 resin, or a 3308 resin.
Preferably, the internal mold release agent is at least one of stearate, fumed silica and vinyl silicone oil; further preferably, the stearate is at least one selected from zinc stearate, calcium stearate, barium stearate, magnesium stearate, aluminum stearate, cadmium stearate, and lead stearate. And the internal release agent is adopted, so that the demolding is easier during demolding.
Preferably, the curing agent is TBPB free radical curing agent, BPO free radical curing agent or 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 certain mechanical strength, and the cross-linked structure can limit the graphene on the surface layer of the conjugated diene resin, so that a barrier layer is formed.
Preferably, the toughening agent is at least one selected from chlorinated polyethylene, chlorosulfonated polyethylene and polychloroprene; still further preferably, the chlorinated polyethylene is CPE135A. The toughening agent, such as chlorinated polyethylene, is used as a thermoplastic material and added into conjugated diene resin (such as dicyclopentadiene), and after being heated (about 70 ℃) and uniformly mixed, the viscosity of the conjugated diene resin and the toughness of a cured product can be improved, so that the graphene modified conjugated diene resin can be molded conveniently.
Preferably, the coupling agent is at least one of KH550, KH560, KH 570. Coupling agents such as KH550, KH560, KH570, etc., which bear a trialkoxy (methoxy or ethoxy) silane group, may be referred to as single-arm silane coupling agents. The silane coupling agent has three crosslinking points generated by the silicon-based part at maximum in the use process, and a three-dimensional network structure is formed in the conjugated diene resin through the crosslinking effect, so that the graphene is limited in the three-dimensional network structure, the compatibility of the graphene and the conjugated diene resin can be improved, and the immiscibility is avoided.
Preferably, the filler is CaCO 3 、Al(OH) 3 、MgCO 3 At least one of them. The fillers such as calcium carbonate and aluminum hydroxide can reinforce the conjugated diene resin, so that the mechanical strength of the graphene modified conjugated diene resin is further improved, and particularly the tensile strength and bending strength of the graphene modified conjugated diene resin are improved.
The second aspect of the invention provides a preparation method of the graphene modified conjugated diene resin provided by the first aspect of the invention, which comprises the following steps: and heating and mixing all the raw materials to prepare the graphene modified conjugated diene resin.
Preferably, the preparation method of the graphene modified conjugated diene resin specifically comprises the following steps: mixing dicyclopentadiene resin and chlorinated polyethylene for the first time, and then sequentially adding graphene, a curing agent, an internal mold release agent, a coupling agent and a filler for the second time to prepare the graphene modified conjugated diene resin.
Preferably, the first mixing step and/or the second mixing step is performed using a stirred tank.
Preferably, the mixing temperature of the first mixing step is 55-85 ℃; further preferably, the mixing temperature of the first mixing step is 60-80 ℃; still further preferably, the mixing temperature of the first mixing step is 65 ℃ to 75 ℃.
Preferably, the mixing time of the first mixing step is 20-40 min; further preferably, the mixing time of the first mixing step is 25 to 35 minutes; the mixing time of the first mixing step is 30min.
Preferably, the mixing temperature of the second mixing step is 45-80 ℃; further preferably, the mixing temperature of the second mixing step is 50-70 ℃; still further preferably, the mixing temperature of the second mixing step is 55℃to 65 ℃.
Preferably, the mixing time of the second mixing step is 20-40 min; further preferably, the mixing time of the second mixing step is 25-35 min; the mixing time of the second mixing step is 30min.
The third aspect of the invention provides an application of the graphene modified conjugated diene resin provided by the first aspect of the invention in automobiles, rail transit, infrastructure and ocean engineering.
The fourth aspect of the invention provides a graphene modified conjugated diene resin laminated board, which comprises the graphene modified conjugated diene resin provided by the first aspect of the invention.
Preferably, the graphene-modified conjugated diene resin laminate sheet further comprises glass fibers.
Preferably, the mass percentage of the graphene modified conjugated diene resin is 31% -47%.
Preferably, the graphene modified conjugated diene resin laminated board is prepared by adopting the following preparation method, and graphene modified conjugated diene resin and glass fiber are mixed and formed by hot pressing.
Preferably, the hot press temperature adopted in the hot press forming step is 100-150 ℃; further preferably, the hot press temperature adopted in the hot press forming step is 110-140 ℃; still further preferably, the hot press temperature used in the hot press molding step is 110℃to 130 ℃.
Preferably, the hot press molding step adopts a hot press time of 20-40 min; further preferably, the hot press molding step adopts a hot press time of 25-35 min; still further preferably, the hot press molding step employs a hot press time of 30 minutes.
Preferably, the glass fiber has an areal density of 400gsm.
Preferably, the graphene-modified conjugated diene resin laminate is at least one of a laminate for an offshore power generation platform, a laminate for an ocean floating island, and a laminate for an offshore oil drilling platform.
The graphene modified conjugated diene resin laminated board can be used for a long time in a high-salt-fog marine environment, solves the problems of short service cycle and easy corrosion failure of unsaturated conjugated diene resin in the marine environment, and has wide application prospects and application values in offshore power generation platforms, ocean floating islands and offshore oil drilling platforms.
The beneficial effects of the invention are as follows: the graphene modified conjugated diene resin has excellent corrosion resistance, and the mechanical strength retention rate is above 85% after the severe grade 5 corrosion performance test, so that the mechanical strength meets the use requirements of materials for automobiles, rail transit, infrastructure and ocean engineering. Meanwhile, the graphene modified conjugated diene resin disclosed by the invention is low in viscosity, has surface air-drying property and is suitable for large-scale prepreg production.
According to the preparation method disclosed by the invention, the graphene is added into the conjugated diene resin through physical blending, the preparation method is simple and easy to operate, the raw materials are low in price and rich in source, and the preparation method is suitable for mass popularization and application.
Drawings
FIG. 1 is an SEM image of a graphene-modified dicyclopentadiene resin of example 1;
FIG. 2 is a graph showing the tensile strength properties of the laminate of comparative example 1 after salt spray corrosion;
FIG. 3 is a graph showing the tensile strength properties of the laminate of example 1 after salt spray corrosion;
FIG. 4 is a graph showing the tensile strength properties of the laminate of example 2 after salt spray corrosion;
FIG. 5 is a graph showing the flexural strength properties of the laminate of comparative example 1 after salt spray corrosion;
FIG. 6 is a graph showing the flexural strength properties of the laminate after salt spray corrosion in example 1;
FIG. 7 is a graph showing the flexural strength properties of the laminate after salt spray corrosion in example 2;
fig. 8 is a structure of graphene-modified dicyclopentadiene resin in example 1.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to the drawings and examples, but the practice and protection of the present invention are not limited thereto. It should be noted that the following processes, unless otherwise specified, are all realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
The graphene modified dicyclopentadiene resin in the example is prepared from the following components in parts by weight: 100 parts of dicyclopentadiene resin, 3 parts of chlorinated polyethylene, 2 parts of graphene and 1 part of gas phase SiO 2 5 parts MgO, 45 parts Al (OH) 3 1 part of zinc stearate, 1 part of KH570, 0.5 part 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, and comprises the following steps:
100 parts of dicyclopentadiene resin and 3 parts of chlorinated polyethylene are stirred and mixed for 30min at 70 ℃, and then 2 parts of graphene and 1 part of gas phase SiO are added in sequence at 60 DEG C 2 5 parts MgO, 45 parts Al (OH) 3 1 part of zinc stearate, 1 part of KH570, 0.5 part of vinyl silicone oil and 1.5 parts of TBPB (t-butylperbenzoate) radical curing agent, and mixing for 20min to prepare the graphene-modified dicyclopentadiene resin in this example.
When SEM images of the graphene-modified dicyclopentadiene resin prepared in this example are tested, see fig. 1 in particular, it can be seen that the graphene in fig. 1 is distributed on the surface of the dicyclopentadiene resin in a layered form.
According to the invention, graphene is added into dicyclopentadiene resin through physical blending, and the graphene is easy to migrate to the surface of a material in the dicyclopentadiene resin due to low polarity, small size effect, high specific strength and large specific surface area of the graphene. Meanwhile, in the high-temperature curing process of the dicyclopentadiene resin, the viscosity of the resin is reduced, the migration energy barrier of graphene is reduced, and finally, a barrier layer enriched in graphene stacking is formed on the surface of the dicyclopentadiene resin along with the curing of the dicyclopentadiene resin. In addition, the formation of the crosslinked structure after the dicyclopentadiene resin is cured has a stabilizing effect on the enrichment of the surface graphene, and the structure of the dicyclopentadiene resin and the graphene as shown in fig. 8 is formed. The surface layer of the dicyclopentadiene resin condensate has high graphene content, and the graphene sheets are stacked, so that the dicyclopentadiene resin condensate has a barrier effect on water vapor with high corrosion content, and prevents corrosion inside materials.
Example 2
The graphene modified dicyclopentadiene resin in the example is prepared from the following components in parts by weight: 100 parts of dicyclopentadiene resin, 3 parts of chlorinated polyethylene, 4 parts of graphene and 1 part of gas phase SiO 2 5 parts MgO, 45 parts Al (OH) 3 1 part of zinc stearate, 1 part of KH570, 0.5 part 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, and comprises the following steps:
100 parts of dicyclopentadiene resin and 3 parts of chlorinated polyethylene are stirred and mixed for 30min at 70 ℃, and then 4 parts of graphene and 1 part of gas phase SiO are added in sequence at 60 DEG C 2 1 part KH570, 5 parts MgO, 45 parts Al (OH) 3 The graphene-modified dicyclopentadiene resin in this example was prepared by mixing 1 part of zinc stearate, 0.5 part of vinyl silicone oil and 1.5 parts of TBPB (t-butyl perbenzoate) radical curing agent for 20 minutes.
Comparative example 1
This example differs from example 1 in that: in this example, the dicyclopentadiene resin in this example was produced by the production method in example 1 without containing graphene.
Performance test:
the resins prepared in example 1, example 2 and comparative example 1 were each used with an areal density of 400gsm (g/cm 2 ) The glass fiber scrim of (c) was mixed to prepare a prepreg, and then cured at 120 ℃ for 30min by a molding process to obtain a dicyclopentadiene resin laminate having a solid content of 39%, and the dicyclopentadiene resin laminate was sampled into dumbbell-shaped tensile bars and bending bars, and then the laminates prepared in example 1, example 2, and comparative example 1 were tested for tensile strength, bending strength, and corrosion resistance, respectively. Wherein the flexural strength and tensile strength are measured according to the methods described in ASTM D7264 and ASTM D3039The tensile strength and flexural strength results obtained by the tests of example 1, example 2 and comparative example 1 are recorded in table 1 below.
Then, the dumbbell type dicyclopentadiene resin laminates prepared in example 1, example 2 and comparative example 1 were subjected to a salt spray corrosion test, and specific test results are shown in fig. 2 to 7. The tensile strength of the laminate obtained in comparative example 1 after salt spray corrosion is shown in FIG. 2, and the flexural strength is shown in FIG. 5. Wherein, in fig. 2, curve (b), curve (a), curve (c), curve (e) and curve (d) are respectively the tensile strength curves of the laminate in the non-proceeding, proceeding 1 time, proceeding 2 times, proceeding 3 times and proceeding 4 times salt spray test cycle; curve (b), curve (a), curve (c), curve (d) and curve (e) in fig. 5 are the bending strength curves of the laminate in the non-run, run 1 time, run 2 times, run 3 times, run 4 times salt spray test cycles, respectively; the tensile strength of the laminate obtained in example 1 after salt spray corrosion is shown in FIG. 3 and the flexural strength is shown in FIG. 6. Wherein, in fig. 3, curve (b), curve (a), curve (e), curve (d) and curve (c) are the tensile strength curves of the laminated board when the laminated board is not processed, processed 1 time, processed 2 times, processed 3 times and processed 4 times of salt spray test cycles; in fig. 6, curves (a), (c), (b), (d) and (e) are bending strength curves of the laminate when the salt spray test cycle was not performed, performed 1 time, performed 2 times, performed 3 times and performed 4 times. The tensile strength of the laminate obtained in example 2 after salt spray corrosion is shown in FIG. 4 and the flexural strength is shown in FIG. 7. In fig. 4, curves (a), (b), (d), (e) and (c) are tensile strength curves of the laminate when the salt spray test is not performed, performed 1 time, performed 2 times, performed 3 times and performed 4 times; in fig. 7, curves (a), (b), (c), (d) and (e) are bending strength curves of the laminate when the salt spray test was not performed, performed 1 time, performed 2 times, performed 3 times and performed 4 times.
The salt spray corrosion test method and the conditions are as follows:
salt spray corrosion tests are tested according to GB/T2423.18-2012 standard, and salt spray treatment conditions are as follows: the solution used is 5% NaCl solution, the precipitation amount of salt fog: 1-2mL/80cm 2 /h, during the treatmentAnd 2h. The wet heat storage conditions are as follows: the temperature of the test box is 40 ℃, the humidity is 93 percent RH, the test time is 22 hours, the salt fog treatment and the damp-heat storage are circulated four times, and the total treatment time is 4 days. After the completion of the test, the test was carried out at 23 ℃ ±2 ℃ for 72 hours under 45%rh to 55%rh (RH is relative humidity), the total test period was 7 days, and the salt spray corrosion test of one cycle was completed, and the tensile and bending properties of the dumbbell-type dicyclopentadiene resin laminates prepared in test example 1, example 2 and comparative example 1 were taken out, and the test results were recorded in table 1 below. The laminates prepared in example 1, example 2 and comparative example 1, which underwent one cycle of salt spray corrosion test, were subjected to a second cycle of salt spray corrosion test, and then were taken out to test tensile and flexural properties, and the test results are recorded in table 1 below. The dumbbell type dicyclopentadiene resin laminates prepared in example 1, example 2 and comparative example 1, which underwent the salt spray corrosion test of two cycles, were subjected to the salt spray corrosion test of the third cycle, and then were taken out to test tensile and flexural properties, and the test results are recorded in table 1 below. The dumbbell type dicyclopentadiene resin laminates prepared in example 1, example 2 and comparative example 1, which underwent the salt spray corrosion test for three cycles, were subjected to the salt spray corrosion test for the fourth cycle, and then were taken out to test tensile and bending properties, and the test results are recorded in table 1 below. The total test duration of four cycles of salt spray corrosion test was 28 days, reaching the severity level (5), while the corrosion resistance properties of dicyclopentadiene resins were characterized by tensile and flexural property decay, with the specific results shown in table 1 below:
TABLE 1 flexural Strength and tensile Strength test results
From table 1 above, it is seen that the dicyclopentadiene laminated board without graphene in comparative example 1 had a tensile strength reduced by 8.25% and a bending strength reduced by 3.49% after 1 salt spray corrosion test period. In example 1, 2 parts of graphene was added to the modified dicyclopentadiene laminated board, the tensile strength was reduced by 4.06%, and the bending strength was reduced by 2.87%. In example 2, the tensile strength of the modified dicyclopentadiene laminated board added with 4 parts of graphene is reduced by 3.77%, and the bending strength is reduced by 1.86%, which indicates that the addition of the lamellar graphene improves the corrosion resistance of the dicyclopentadiene laminated board.
After 2 salt spray corrosion test cycles, the dicyclopentadiene laminated board without added graphene in comparative example 1 had a 16.90% decrease in tensile strength and a 9.61% decrease in flexural strength. In example 1, 2 parts of graphene was added to the dicyclopentadiene laminated board, the tensile strength was reduced by 8.20%, and the bending strength was reduced by 5.99%. In example 2, the tensile strength of the dicyclopentadiene laminated board added with 4 parts of graphene was reduced by 6.92%, and the bending strength was reduced by 4.14%.
After 3 salt spray corrosion test cycles, the dicyclopentadiene laminated board without added graphene in comparative example 1 had a 27.81% decrease in tensile strength and 18.23% decrease in flexural strength. In example 1, the tensile strength of the dicyclopentadiene laminated board added with 2 parts of graphene was reduced by 11.00% and the bending strength was reduced by 10.43%. In example 2, the tensile strength of the dicyclopentadiene laminated board added with 4 parts of graphene was reduced by 9.13%, and the bending strength was reduced by 6.89%.
After 4 salt spray corrosion test cycles, the dicyclopentadiene laminated board without added graphene in comparative example 1 had a 36.91% decrease in tensile strength and a 28.71% decrease in flexural strength. In example 1, 2 parts of graphene was added to the dicyclopentadiene laminated board, the tensile strength was reduced by 14.96%, and the bending strength was reduced by 14.85%. In example 2, the tensile strength of the dicyclopentadiene laminated board added with 4 parts of graphene was reduced by 11.69%, and the bending strength was reduced by 9.32%.
From the above analysis, it was found that the mechanical properties of the dicyclopentadiene laminate prepreg of comparative example 1 were gradually decreased with the increase in corrosion time, because the inner layer of the material was corroded and a wick diffusion effect occurred, resulting in the increase in corrosion of the material. The mechanical properties of the dicyclopentadiene laminated plates in the examples 1 and 2 after the graphene is added are reduced, because the modification of the graphene has an isolation effect on the surface layer of the dicyclopentadiene laminated plate, the corrosion of the corrosion component on the inner layer of the material is blocked, and the mechanical properties are obviously reduced compared with those of the dicyclopentadiene laminated plates without the graphene. When the graphene addition amount is increased from 2 parts to 4 parts, the performance retention rate is improved to a certain extent, but the improvement range is lower.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (6)
1. A graphene modified conjugated diene resin is characterized in that: the graphene-based conjugated diene resin comprises conjugated diene resin and graphene, wherein the conjugated diene resin comprises at least one of dicyclopentadiene resin and tricyclopentadiene resin;
the graphene modified conjugated diene resin further comprises at least one of a curing agent, a coupling agent, an internal mold release agent, a filler and a toughening agent;
the mass ratio of the graphene to the conjugated diene resin is (1-4): 100;
the conjugated diene resin: the mass ratio of the curing agent is 100: (1-2);
the conjugated diene resin: the mass ratio of the toughening agent is 100: (3-3.5);
the conjugated diene resin: the mass ratio of the internal mold release agent is 100:1, a step of;
the conjugated diene resin: the mass ratio of the coupling agent is 100:1, a step of;
the conjugated diene resin: the mass ratio of the filler is 100: (45-50);
the coupling agent is KH570;
the preparation method of the graphene modified conjugated diene resin comprises the following steps:
mixing conjugated diene resin and a toughening agent for the first time, and then sequentially adding graphene, a curing agent, an internal release agent, a coupling agent and a filler for the second time to prepare graphene modified conjugated diene resin;
the first mixing and the second mixing adopt a physical blending mode.
2. The graphene-modified conjugated diene resin according to claim 1, wherein: the graphene is of a lamellar structure.
3. The graphene-modified conjugated diene resin according to claim 1, wherein: the internal release agent is at least one of stearate, fumed silica and vinyl silicone oil.
4. The graphene-modified conjugated diene resin according to claim 1, wherein: the toughening agent is at least one of chlorinated polyethylene, chlorosulfonated polyethylene and polychloroprene.
5. The graphene-modified conjugated diene resin according to claim 1, wherein: the curing agent is TBPB free radical curing agent.
6. Use of the graphene-modified conjugated diene resin according to any one of claims 1 to 5 in automobiles, rail transit, ocean engineering.
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| CN112961279B (en) * | 2021-02-10 | 2022-10-21 | 浙江沪通模具有限公司 | Polyttricyclopentadiene PTCPD and polydicyclopentadiene PDCPD copolymer and preparation method thereof |
| CN112812487A (en) * | 2021-02-10 | 2021-05-18 | 浙江沪通模具有限公司 | Carbon nano tube modified polytriacyclopentadiene PTCPD composite material and preparation method thereof |
| CN112961453A (en) * | 2021-03-12 | 2021-06-15 | 浙江沪通模具有限公司 | Polytriacyclopentadiene PTCPD/elastomer IPN alloy material and preparation method thereof |
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| CN114031880A (en) | 2022-02-11 |
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