A wear-resistant rubber based on modified graphene oxide and preparation method thereof

Abstract

The present invention discloses a wear-resistant rubber based on modified graphene oxide and a preparation method thereof. The wear-resistant rubber comprises the following components: 100 parts by weight of fluororubber, 0.8 to 3.2 parts by weight of a vulcanizing agent, 0.2 to 1.6 parts by weight of an accelerator, 10 to 32 parts by weight of modified graphene oxide, 6 to 11 parts by weight of glass fiber, and 0.6 to 1.8 parts by weight of hydroxy silicone oil. The present invention introduces an organic fluorine monomer having a vinyl group into the graphene oxide, and through grafting modification, improves the dispersion uniformity of the graphene oxide in the fluororubber product, thereby enhancing the product's performance uniformity and stability.

Description

Technical Field

[0001] The present invention relates to the technical field of wear-resistant rubber, and in particular to a wear-resistant rubber based on modified graphene oxide and a preparation method thereof. Background Art

[0002] As the variety of rubber types increases, the application range of rubber products is becoming increasingly broad. Wear-resistant rubber, as one of the existing rubber types, is primarily used in high-wear interfaces to support objects or protect key equipment components. Therefore, as a raw material for the production of wear-resistant parts, wear-resistant rubber should exhibit high product performance uniformity and stability, as well as good wear resistance. However, due to compatibility issues, the dispersion uniformity of some additives in wear-resistant rubber products is affected to a certain extent, which in turn has a certain impact on product performance. Summary of the Invention

[0003] To this end, the technical problem to be solved by the present invention is to provide a wear-resistant rubber based on modified graphene oxide and a preparation method thereof, by introducing an organic fluorine monomer with a vinyl group into the graphene oxide, and through grafting modification, improving the dispersion uniformity of the graphene oxide in the fluororubber product, thereby improving the performance uniformity and stability of the product.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] A wear-resistant rubber based on modified graphene oxide, comprising the following components: 100 parts by weight of fluororubber, 0.8 to 3.2 parts by weight of a vulcanizing agent, 0.2 to 1.6 parts by weight of an accelerator, 10 to 32 parts by weight of modified graphene oxide, 6 to 11 parts by weight of glass fiber, and 0.6 to 1.8 parts by weight of hydroxy silicone oil; wherein the modified graphene oxide is prepared by the following steps:

[0006] a) preparing materials: preparing raw materials according to the following components: 20 to 50 parts by weight of graphene oxide, 4 to 13 parts by weight of hydroxylated carbon nanotubes, and 7 to 18 parts by weight of an organic fluorine monomer having a vinyl structure;

[0007] b) dispersing the graphene oxide and hydroxylated graphene obtained in step a) in ethanol by ultrasonication to obtain a first mixed solution;

[0008] c) adding the organic fluorine monomer to the first mixed solution prepared in step b), stirring and mixing to obtain a second mixed solution;

[0009] d) Place the second mixed solution in 60 The modified graphene oxide is irradiated in a Co radioactive source with an absorbed dose of 10 to 800 kGy, and then filtered and dried to obtain the modified graphene oxide.

[0010] In the above-mentioned wear-resistant rubber based on modified graphene oxide, the organic fluorine monomer is one or more of vinyl fluoride, vinylidene fluoride and p-fluorostyrene.

[0011] In the above-mentioned wear-resistant rubber based on modified graphene oxide, the hydroxylated carbon nanotubes are hydroxylated single-walled carbon nanotubes or hydroxylated multi-walled carbon nanotubes or a mixture of the two.

[0012] In the above-mentioned wear-resistant rubber based on modified graphene oxide, the hydroxylated carbon nanotubes are composed of 20 to 30 parts by weight of hydroxylated single-walled carbon nanotubes and 5 to 15 parts by weight of hydroxylated multi-walled carbon nanotubes.

[0013] In the above-mentioned wear-resistant rubber based on modified graphene oxide, the vulcanizing agent is N,N'-biscinnamaldehyde-1,6-hexanediamine, and the accelerator is benzyltriphenylphosphonium chloride.

[0014] The above-mentioned wear-resistant rubber based on modified graphene oxide, the fluororubber is one of a copolymer of vinylidene fluoride and chlorotrifluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, or a terpolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene.

[0015] The above-mentioned wear-resistant rubber based on modified graphene oxide, the copolymer of vinylidene fluoride and chlorotrifluoroethylene is fluororubber 23; the copolymer of vinylidene fluoride and hexafluoropropylene is fluororubber 26; the ternary copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene is fluororubber 246.

[0016] In the above-mentioned wear-resistant rubber based on modified graphene oxide, in step d), before irradiating the second mixed liquid, the second mixed liquid is first cooled to 5-10° C., and the second mixed liquid is irradiated at room temperature.

[0017] The preparation method of the above-mentioned wear-resistant rubber based on modified graphene oxide comprises the following steps:

[0018] 1) preparing materials according to the following formula: 100 parts by weight of fluororubber, 0.8 to 3.2 parts by weight of a vulcanizing agent, 0.2 to 1.6 parts by weight of an accelerator, 10 to 32 parts by weight of modified graphene oxide, 6 to 11 parts by weight of glass fiber, and 0.6 to 1.8 parts by weight of hydroxy silicone oil;

[0019] 2) refining the fluororubber, modified graphene oxide, glass fiber and hydroxy silicone oil in an open mill, adding the vulcanizing agent and accelerator after refining for 10 to 15 minutes, and continuing to refining until the mixture is uniform to obtain a rubber mix, the refining temperature being 49 to 51° C.;

[0020] 3) Place the mixed rubber in a vulcanizer for vulcanization at a temperature of 160-200°C and a vulcanization time of 10-20 minutes.

[0021] The above preparation method is characterized in that the vulcanization is divided into two stages. In the first stage, the vulcanization temperature is 160-170°C and the vulcanization time is 3-7 minutes; in the second stage, the vulcanization temperature is 190-200°C and the vulcanization time is 10-12 minutes.

[0022] The technical solution of the present invention achieves the following beneficial technical effects:

[0023] The present invention utilizes hydroxylated carbon nanotubes to perform an intercalation-type spatial structural change on graphene oxide, and then uses an organic fluorine monomer with a vinyl structure to modify the graphene oxide and the hydroxylated carbon nanotubes to prepare modified graphene oxide. This improves the dispersion uniformity of the graphene oxide and the hydroxylated carbon nanotubes in fluororubber, thereby improving the performance uniformity of wear-resistant rubber products and using less graphene oxide while ensuring the same quality. DETAILED DESCRIPTION

[0024] Example 1

[0025] In this embodiment, the wear-resistant rubber based on modified graphene oxide is composed of the following components: 100 parts by weight of fluororubber, 0.8 parts by weight of a vulcanizing agent, 0.2 parts by weight of an accelerator, 10 parts by weight of modified graphene oxide, 6 parts by weight of glass fiber, and 0.6 parts by weight of hydroxy silicone oil. The fluororubber is fluororubber 246, the vulcanizing agent is N,N'-biscinnamaldehyde-1,6-hexanediamine acetal, and the accelerator is benzyltriphenylphosphonium chloride.

[0026] Wherein, the modified graphene oxide is prepared by the following steps:

[0027] a) preparing materials: preparing raw materials according to the following components: 20 parts by weight of graphene oxide, 4 parts by weight of hydroxylated carbon nanotubes, and 7 parts by weight of an organic fluorine monomer having a vinyl structure; wherein the hydroxylated carbon nanotubes are hydroxylated single-walled carbon nanotubes, and the organic fluorine monomer having a vinyl structure is vinylidene fluoride;

[0028] b) dispersing the graphene oxide and hydroxylated graphene obtained in step a) in ethanol by ultrasonication to obtain a first mixed solution;

[0029] c) adding the organic fluorine monomer to the first mixed solution prepared in step b), stirring and mixing to obtain a second mixed solution;

[0030] d) Place the second mixed solution in 60 The modified graphene oxide was irradiated in a Co radioactive source with an absorbed dose of 10 kGy, and then filtered and dried to obtain the modified graphene oxide.

[0031] Wear-resistant rubber based on modified graphene oxide was prepared by the following steps:

[0032] 1) preparing materials according to the following formula: 100 parts by weight of fluororubber, 0.8 parts by weight of vulcanizing agent, 0.2 parts by weight of accelerator, 10 parts by weight of modified graphene oxide, 6 parts by weight of glass fiber, and 0.6 parts by weight of hydroxy silicone oil;

[0033] 2) refining the fluororubber, modified graphene oxide, glass fiber and hydroxy silicone oil in an open mill, adding the vulcanizing agent and accelerator after refining for 10 minutes, and continuing to refining until the mixture is uniform to obtain a rubber mix, the refining temperature is 49-51°C;

[0034] 3) Place the mixed rubber in a vulcanizer for vulcanization at a temperature of 160°C and a vulcanization time of 10 minutes.

[0035] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 1.

[0036] Example 2

[0037] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the hydroxylated carbon nanotubes are hydroxylated multi-walled carbon nanotubes.

[0038] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 2.

[0039] Example 3

[0040] In this embodiment, the wear-resistant rubber based on modified graphene oxide differs from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the hydroxylated carbon nanotubes are composed of 20 parts by weight of hydroxylated single-walled carbon nanotubes and 5 parts by weight of hydroxylated multi-walled carbon nanotubes.

[0041] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 3.

[0042] Example 4

[0043] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the organic fluorine monomer having a vinyl structure is p-fluorostyrene.

[0044] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 4.

[0045] Example 5

[0046] In this embodiment, the wear-resistant rubber based on modified graphene oxide differs from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the organic fluorine monomer having a vinyl structure is a mixture of vinylidene fluoride and para-fluorostyrene in a molar ratio of 1:1.

[0047] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 5.

[0048] Example 6

[0049] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the amount of modified graphene oxide used is 32 parts by weight.

[0050] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 6.

[0051] Example 7

[0052] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the amount of modified graphene oxide used is 21 parts by weight.

[0053] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 7.

[0054] Example 8

[0055] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the amount of the organic fluorine monomer having a vinyl structure used in preparing the modified graphene oxide is 18 parts by weight.

[0056] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 8.

[0057] Example 9

[0058] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the amount of the organic fluorine monomer having a vinyl structure used in preparing the modified graphene oxide is 13 parts by weight.

[0059] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 9.

[0060] Example 10

[0061] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the amount of hydroxylated carbon nanotubes used in preparing the modified graphene oxide is 9 parts by weight.

[0062] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 10.

[0063] Example 11

[0064] In this embodiment, the wear-resistant rubber based on modified graphene oxide is different from the wear-resistant rubber based on modified graphene oxide in Example 1 in that the amount of hydroxylated carbon nanotubes used in preparing the modified graphene oxide is 13 parts by weight.

[0065] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 11.

[0066] Example 12

[0067] In this embodiment, the wear-resistant rubber based on modified graphene oxide is composed of the following components: 100 parts by weight of fluororubber, 2.3 parts by weight of a vulcanizing agent, 1.1 parts by weight of an accelerator, 29 parts by weight of modified graphene oxide, 9 parts by weight of glass fiber, and 1.3 parts by weight of hydroxy silicone oil. The vulcanizing agent is N,N'-biscinnamaldehyde 1,6-hexanediamine acetal, and the accelerator is benzyltriphenylphosphonium chloride.

[0068] Wherein, the modified graphene oxide is prepared by the following steps:

[0069] a) Preparation of materials: preparing raw materials according to the following components: 42 parts by weight of graphene oxide, 11 parts by weight of hydroxylated carbon nanotubes, and 14 parts by weight of an organic fluorine monomer having a vinyl structure; wherein the hydroxylated carbon nanotubes are composed of 26 parts by weight of hydroxylated single-walled carbon nanotubes and 11 parts by weight of hydroxylated multi-walled carbon nanotubes, and the organic fluorine monomer having a vinyl structure is a mixture of vinylidene fluoride and paraphenylene fluoride in a molar ratio of 2:1;

[0070] b) dispersing the graphene oxide and hydroxylated graphene obtained in step a) in ethanol by ultrasonication to obtain a first mixed solution;

[0071] c) adding the organic fluorine monomer to the first mixed solution prepared in step b), stirring and mixing to obtain a second mixed solution;

[0072] d) Place the second mixed solution in 60 The second mixed solution was irradiated in a Co radioactive source with an absorbed dose of 750 kGy, and then filtered and dried to obtain modified graphene oxide; before the second mixed solution was irradiated, the second mixed solution was cooled to 5-10° C., and the second mixed solution was irradiated at room temperature, which was 25° C.

[0073] Wear-resistant rubber based on modified graphene oxide was prepared by the following steps:

[0074] 1) preparing materials according to the following formula: 100 parts by weight of fluororubber, 2.3 parts by weight of vulcanizing agent, 1.1 parts by weight of accelerator, 29 parts by weight of modified graphene oxide, 9 parts by weight of glass fiber, and 1.3 parts by weight of hydroxy silicone oil;

[0075] 2) refining the fluororubber, modified graphene oxide, glass fiber and hydroxy silicone oil in an open mill, adding the vulcanizing agent and accelerator after refining for 15 minutes, and continuing to refining until the mixture is uniform to obtain a rubber mix, the refining temperature is 49-51°C;

[0076] 3) The mixed rubber is vulcanized in a vulcanizer. In the first stage, the vulcanization temperature is 160-170°C and the vulcanization time is 5 minutes; in the second stage, the vulcanization temperature is 190-200°C and the vulcanization time is 12 minutes.

[0077] The wear-resistant rubber based on modified graphene oxide prepared in this example is named Sample 12.

[0078] Comparative Example 1

[0079] The difference between the wear-resistant rubber in this embodiment and the wear-resistant rubber based on modified graphene oxide in Example 12 is that the graphene oxide and the hydroxylated carbon nanotubes are not subjected to ultrasonic dispersion and modification treatment with an organic fluorine monomer having a vinyl structure, but are directly used as additives.

[0080] The wear-resistant rubber prepared in this example is named as a comparative sample.

[0081] The wear-resistant rubber based on modified graphene oxide prepared in Examples 1 to 12 and the wear-resistant rubber prepared in the comparative example were subjected to performance tests. The results are shown in Table 1. The specific test method is as follows:

[0082] Tensile strength and elongation at break refer to: GB / T 528-2009;

[0083] Shore A hardness reference: GB / T 531.1-2008;

[0084] Compression set rate refers to standard GB / T 7759-1996;

[0085] Wear resistance (Akron abrasion testing machine) reference standard GB / T 1689-2014.

[0086] Table 1 Comparison of rubber properties

[0087]

[0088] It can be seen from the data recorded in Table 1 that, compared with the wear-resistant rubber prepared in the comparative example, the tensile strength and elongation at break of the wear-resistant rubber based on modified graphene oxide in Examples 1 to 12 are significantly improved, the compression set rate and Akron wear volume are significantly reduced, and the Shore A hardness is also improved.

[0089] Furthermore, it can be seen from the data recorded in Table 1 that when the amount of graphene oxide and hydroxylated carbon nanotubes is constant, the modified graphene oxide obtained by increasing the amount of organic fluorine monomer with a vinyl structure improves the performance of the wear-resistant rubber based on graphene oxide. The reason is that after the amount of organic fluorine monomer with a vinyl structure is increased, the length of the polymer molecular chain grafted on graphene oxide and hydroxylated carbon nanotubes increases, and during the mixing process, the polymer molecular chains grafted on graphene oxide and hydroxylated carbon nanotubes are more likely to be entangled with the molecular chains of fluororubber, and during vulcanization, it is easier to form a three-dimensional cross-linked network. At the same time, the length of the polymer molecular chains grafted on graphene oxide and hydroxylated carbon nanotubes is within a certain range, and the polymer molecular chains grafted on graphene oxide and hydroxylated carbon nanotubes have a positive effect on the elongation at break of the wear-resistant rubber based on graphene oxide.

[0090] According to the formula and preparation method described in Example 12, a total of 7 samples were prepared and performance tests were performed on the samples. The deviation rate between the performance of the 7 samples tested and the data described in the table did not exceed 3%.

[0091] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the claims of this patent application.

Claims

1. A wear-resistant rubber based on modified graphene oxide, characterized in that, The invention comprises the following components: 100 parts by weight of fluororubber, 0.8 to 3.2 parts by weight of a vulcanizing agent, 0.2 to 1.6 parts by weight of an accelerator, 10 to 32 parts by weight of modified graphene oxide, 6 to 11 parts by weight of glass fiber, and 0.6 to 1.8 parts by weight of hydroxy silicone oil; wherein the modified graphene oxide is prepared by the following steps: a) preparing materials: preparing raw materials according to the following components: 20 to 50 parts by weight of graphene oxide, 4 to 13 parts by weight of hydroxylated carbon nanotubes, and 7 to 18 parts by weight of an organic fluorine monomer having a vinyl structure; b) dispersing the graphene oxide and hydroxylated graphene obtained in step a) in ethanol by ultrasonication to obtain a first mixed solution; c) adding the organic fluorine monomer to the first mixed solution prepared in step b), stirring and mixing to obtain a second mixed solution; d) Place the second mixed solution in 60 The modified graphene oxide is irradiated in a Co radioactive source with an absorbed dose of 10 to 800 kGy, and then filtered and dried to obtain the modified graphene oxide.

2. The wear-resistant rubber based on modified graphene oxide according to claim 1, characterized in that The organic fluorine monomer is one or more of vinyl fluoride, vinylidene fluoride and p-fluorostyrene.

3. The wear-resistant rubber based on modified graphene oxide according to claim 1, characterized in that The hydroxylated carbon nanotubes are hydroxylated single-walled carbon nanotubes or hydroxylated multi-walled carbon nanotubes or a mixture of the two.

4. The wear-resistant rubber based on modified graphene oxide according to claim 3, characterized in that The hydroxylated carbon nanotubes are composed of 20 to 30 parts by weight of hydroxylated single-walled carbon nanotubes and 5 to 15 parts by weight of hydroxylated multi-walled carbon nanotubes.

5. The wear-resistant rubber based on modified graphene oxide according to claim 1, characterized in that The vulcanizing agent is N,N'-dicinnamaldehyde-1,6-hexanediamine, and the accelerator is benzyltriphenylphosphonium chloride.

6. The wear-resistant rubber based on modified graphene oxide according to claim 1, characterized in that The fluororubber is one of a copolymer of vinylidene fluoride and chlorotrifluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, or a terpolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene.

7. The wear-resistant rubber based on modified graphene oxide according to claim 6, characterized in that The copolymer of vinylidene fluoride and chlorotrifluoroethylene is fluororubber 23; the copolymer of vinylidene fluoride and hexafluoropropylene is fluororubber 26; the ternary copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene is fluororubber 246.

8. The wear-resistant rubber based on modified graphene oxide according to claim 1, characterized in that: In step d), before irradiating the second mixed solution, the second mixed solution is first cooled to 5-10° C., and the second mixed solution is irradiated at room temperature.

9. The method for preparing the wear-resistant rubber based on modified graphene oxide according to claim 1, characterized in that: The steps include: 1) preparing materials according to the following formula: 100 parts by weight of fluororubber, 0.8 to 3.2 parts by weight of a vulcanizing agent, 0.2 to 1.6 parts by weight of an accelerator, 10 to 32 parts by weight of modified graphene oxide, 6 to 11 parts by weight of glass fiber, and 0.6 to 1.8 parts by weight of hydroxy silicone oil; 2) refining the fluororubber, modified graphene oxide, glass fiber and hydroxy silicone oil in an open mill, adding the vulcanizing agent and accelerator after refining for 10 to 15 minutes, and continuing to refining until the mixture is uniform to obtain a rubber mix, the refining temperature being 49 to 51° C.; 3) Place the mixed rubber in a vulcanizer for vulcanization at a temperature of 160-200°C and a vulcanization time of 10-20 minutes.

10. The preparation method according to claim 9, characterized in that: Vulcanization is divided into two stages. In the first stage, the vulcanization temperature is 160-170°C and the vulcanization time is 3-7 minutes. In the second stage, the vulcanization temperature is 190-200°C and the vulcanization time is 10-12 minutes.

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