Preparation method of high-strength high-toughness low-energy-consumption low-heat-generation rubber and high-strength high-toughness low-energy-consumption low-heat-generation rubber

Abstract

The invention relates to a preparation method of high-strength, high-toughness, low-energy-consumption and low-heat-generation rubber and the high-strength, high-toughness, low-energy-consumption and low-heat-generation rubber. The preparation method comprises the following steps: blending thermosetting rubber and a vulcanizing agent to obtain a first blend, standing, and carrying out mold pressing vulcanization to obtain a vulcanized rubber sheet; crushing the vulcanized rubber sheet, and then carrying out ball milling treatment to obtain a polymer-based filler; blending the mixture with emulsion polymerized thermosetting rubber; sequentially adding a first vulcanization accelerator, an activating agent, an anti-aging agent, a second vulcanization accelerator, a third vulcanization accelerator and a vulcanizing agent to obtain a rubber compound; and after standing, carrying out mould pressing vulcanization to obtain the high-strength high-toughness low-energy-consumption low-heat-generation rubber. The high-strength, high-toughness, low-energy-consumption and low-heat-generation rubber prepared by the preparation method disclosed by the invention has high strength, high toughness, low energy consumption and low heat generation, and the whole process does not involve complex chemical synthesis and use of toxic reagents and drugs.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber composite materials, and more particularly to a method for preparing a high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber and the high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber obtained by the preparation method. Background Art

[0002] Pure rubber materials often cannot meet the needs of engineering applications due to their low mechanical strength and need to be strengthened with the help of nanomaterials. Existing nanomaterials usually include carbon black, white carbon black, calcium carbonate, clay and other materials. It is reported that more than 80% of rubber products are currently made by reinforcing with nanomaterials. The compounding of traditional inorganic nanomaterials with rubber will face problems such as filler dispersion, poor affinity between filler and rubber, and poor interface bonding between filler and rubber. Taking carbon black as an example, nano-sized carbon black particles have high surface activation energy due to their high specific surface area. They often exist in the rubber matrix in the form of agglomerates, such as Figure 1 The dispersion of fillers in rubber and the interfacial bonding will affect the dynamic and static mechanical properties of the composite material.

[0003] To address the challenges of inorganic nanofillers in rubber matrices, researchers typically use physical methods such as high-energy mixing and ultrasonic treatment, or chemical methods such as adding dispersants and coupling agents to promote uniform dispersion of the fillers within the matrix. While these methods improve filler dispersion within the matrix, these physical methods increase energy consumption in the rubber composite, while chemical methods involve complex chemical synthesis and the use of toxic reagents and drugs.

[0004] Therefore, developing a rubber with high strength, high toughness, low energy consumption and low heat generation has become an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a method for preparing high-strength, high-toughness, low-energy consumption and low-heat generation rubber. The high-strength, high-toughness, low-energy consumption and low-heat generation rubber prepared by the method not only has significant advantages in mechanical enhancement, toughening and dynamic performance, but also the preparation method does not involve complex chemical synthesis and the use of toxic reagents and drugs.

[0006] One of the purposes of the present invention is to provide a method for preparing high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber, the preparation method comprising the following steps:

[0007] S1: blending a thermosetting rubber and a vulcanizing agent to obtain a first blend; wherein the thermosetting rubber is any one of styrene-butadiene rubber, natural rubber, and ethylene-propylene-diene monomer rubber;

[0008] S2: The first blend is allowed to stand, and the curing time t of the first blend is measured. 90 ;

[0009] S3: performing compression vulcanization on the first blend to obtain a vulcanized rubber sheet;

[0010] S4: crushing the vulcanized rubber sheet to obtain a polymer-based filler with an average particle size of 1 to 2.5 μm;

[0011] S5: ball milling the polymer-based filler having an average particle size of 1 to 2.5 μm to obtain a polymer-based filler having an average particle size of 0.3 to 0.6 μm;

[0012] S6: blending the polymer-based filler having an average particle size of 0.3 to 0.6 μm with the emulsion-polymerized thermosetting rubber; sequentially adding a first vulcanization accelerator, an activator, an antioxidant, a second vulcanization accelerator, a third vulcanization accelerator, and a vulcanizing agent to obtain a rubber mixture;

[0013] S7: The rubber mix is allowed to stand and the curing time t of the rubber mix is measured. 90 ;

[0014] S8: The mixed rubber is subjected to molding and vulcanization to obtain a high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber.

[0015] The preparation method may specifically include:

[0016] S1: First, the thermosetting rubber and the vulcanizing agent are blended in a two-roll mill so that the crosslinking agent and the rubber are fully mixed to obtain a first blend.

[0017] S2: After the first blend is allowed to stand for a certain period of time, the positive vulcanization time t of the first blend can be measured by a rotorless vulcanizer. 90 .

[0018] S3: performing compression vulcanization on the first blend using a flat vulcanizing press to obtain a vulcanized rubber sheet.

[0019] S4: Crushing the vulcanized rubber sheet in an open mill for a certain period of time to obtain a polymer-based filler with an average particle size of 1 to 2.5 μm.

[0020] S5: ball-milling the polymer-based filler with an average particle size of 1 to 2.5 μm to obtain a polymer-based filler with an average particle size of 0.3 to 0.6 μm.

[0021] S6: The polymer-based filler with an average particle size of 0.3 to 0.6 μm is blended with the emulsion thermosetting rubber on a two-roll mill, and then a first vulcanization accelerator, an activator, an antioxidant, a second vulcanization accelerator, a third vulcanization accelerator, and a vulcanizing agent are added in sequence to obtain a mixed rubber.

[0022] S7: After the rubber mix has been allowed to stand for a certain period of time, the curing time t of the rubber mix is measured using a rotorless curing instrument. 90 .

[0023] S8: The mixed rubber is subjected to mold vulcanization by a flat vulcanizing machine to obtain a high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber.

[0024] In a preferred embodiment of the present invention, in step S1, the thermosetting rubber is any one of styrene-butadiene rubber, natural rubber, and EPDM rubber; and / or the vulcanizing agent is any one of dicumyl peroxide and sulfur; and / or the weight ratio of the thermosetting rubber to the vulcanizing agent is 100:0.2-2.0, preferably 100:0.25-1.0; and / or the blending time is 10-20 minutes, preferably 10-15 minutes; and / or the blending method is a knife method and / or a triangle bagging method. Technicians can select appropriate thermosetting rubber, vulcanizing agent, weight ratio of thermosetting rubber to vulcanizing agent, blending time, and blending method according to actual needs.

[0025] It should be noted that the knife method involves cutting the rubber from left to right with a knife. When the knife reaches a certain distance to the right, the knife is turned 90 degrees and the rubber sheet is continued to be cut, so that the rubber sheet falls onto the bottom plate. When the accumulated rubber sheet is about to disappear, the rubber sheet is cut and cut again. This process is repeated several times to ensure uniform mixing. The triangle bag method is to cut the rubber sheet on the roller horizontally, then fold the film alternately from left to right towards the center, forming a triangular rubber bag on the front roller, and then push the rubber bag into the roller gap. This process is repeated several times to mix the rubber sheet.

[0026] In a preferred embodiment of the present invention, in step S2, the standing time is 6 to 24 hours, preferably 8 to 12 hours. Technicians can select an appropriate standing time according to actual needs.

[0027] In a preferred embodiment of the present invention, in step S3, the temperature of the compression vulcanization is 150-170°C, preferably 160-165°C; and / or the pressure of the compression vulcanization is 10-15 MPa, preferably 13-15 MPa; and / or the time of the compression vulcanization is t 90 +3 minutes~t 90 +5 minutes, preferably t 90 +3 minutes~t 90 +4 minutes. Technicians can select appropriate temperature, pressure and time for compression vulcanization according to actual needs.

[0028] In a preferred embodiment of the present invention, in step S4, the crushing time is 5 to 20 minutes, preferably 5 to 15 minutes. Technicians can select an appropriate crushing time according to actual particle size requirements.

[0029] In a preferred embodiment of the present invention, in step S5, the ball milling treatment time is 3 to 5 hours, preferably 3 to 4 hours. A skilled person can select an appropriate ball milling treatment time based on actual particle size requirements. Preferably, the ball milling treatment is performed in a planetary ball mill; more preferably, the spherical graphite beads in the planetary ball mill are 0.5 to 2.0 mm in size; and / or the mass ratio of the spherical graphite beads in the planetary ball mill to the polymer-based filler having an average particle size of 0.3 to 0.6 μm is 100 to 200:1.

[0030] In a preferred embodiment of the present invention, in step S6, the first vulcanization accelerator is any one of stearic acid, sodium stearate, and potassium stearate; and / or the activator is any one of zinc oxide, potassium disulfide, and benzoyl peroxide; and / or the second vulcanization accelerator is any one of N-cyclohexyl-2-benzothiazolesulfenamide and dibenzothiazyl disulfide; and / or the third vulcanization accelerator is any one of diphenylguanidine and tetramethylthiuram disulfide; and / or the vulcanizing agent is sulfur; and / or the antioxidant is 4010NA. A skilled person can select the appropriate first vulcanization accelerator, activator, antioxidant, second vulcanization accelerator, and third vulcanization accelerator according to actual needs.

[0031] In a preferred embodiment of the present invention, in step S6, the weight ratio of the emulsion-polymerized thermosetting rubber, the polymer-based filler having an average particle size of 0.3 to 0.6 μm, the first vulcanization accelerator, the activator, the antioxidant, the second vulcanization accelerator, the third vulcanization accelerator, and the vulcanizing agent is 100:10 to 17:0.8 to 1.2:4 to 6:0.8 to 2.0:1.2 to 1.8:1.8 to 2.2:1.0 to 1.6. Technicians can select an appropriate weight ratio of the emulsion-polymerized thermosetting rubber, the polymer-based filler having an average particle size of 0.3 to 0.6 μm, the first vulcanization accelerator, the activator, the antioxidant, the second vulcanization accelerator, the third vulcanization accelerator, and the vulcanizing agent according to actual needs.

[0032] In a preferred embodiment of the present invention, in step S6, the blending time is 10 to 15 minutes; and / or the blending method is a knife method and / or a triangle bag method. A technician can select an appropriate blending time and blending method according to actual needs.

[0033] In a preferred embodiment of the present invention, in step S7, the standing time is 6 to 24 hours, preferably 8 to 12 hours. Technicians can select an appropriate standing time according to actual needs.

[0034] In a preferred embodiment of the present invention, in step S8, the temperature of the compression vulcanization is 143-155°C, preferably 150-155°C; and / or the pressure of the compression vulcanization is 10-15 MPa, preferably 13-15 MPa; and / or the time of the compression vulcanization is t 90 +3 minutes~t 90 +5 minutes, preferably t 90 +3 minutes~t 90 +4 minutes. Technicians can select appropriate temperature, pressure and time for compression vulcanization according to actual needs.

[0035] The second object of the present invention is to provide a high-strength, high-toughness, low-energy consumption, low-heat generation rubber obtained by the preparation method of the high-strength, high-toughness, low-energy consumption, low-heat generation rubber according to the first object of the present invention.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. The high-strength, high-toughness, low-energy consumption, and low-heat generation rubber prepared by the preparation method of the present invention has significant advantages in mechanical enhancement, toughening, and dynamic performance, and has high strength, high toughness, low energy consumption, and low heat generation.

[0038] 2. The method for preparing the high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber of the present invention does not involve complicated chemical synthesis and the use of toxic reagents and drugs. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a schematic diagram of the shapes of carbon black aggregates in rubber in the prior art;

[0040] Figure 2 The SEM images and particle size distribution diagrams of the polymer-based fillers prepared in Examples 1 to 3 of the present invention are shown;

[0041] Figure 3 The uniaxial tensile stress-strain curves of the high-strength, high-toughness, low-energy-consumption, low-heat-generation rubber prepared in Test Example 1 of the present invention and the rubbers prepared in Comparative Examples 1 and 2;

[0042] Figure 4 This is a statistical comparison chart of the toughness of the high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber prepared in Test Example 1 of the present invention and the rubbers prepared in Comparative Examples 1 and 2;

[0043] Figure 5 The cyclic stretch-recovery curves of the high-strength, high-toughness, low-energy-consumption, low-heat-generation rubber prepared in Test Example 1 of the present invention and the rubbers prepared in Comparative Examples 1 and 2 are shown;

[0044] Figure 6Schematic diagram of the percentage of hysteresis energy loss during cyclic stretching of the high-strength, high-toughness, low-energy consumption, and low-heat generation rubber prepared in Test Example 1 of the present invention and the rubbers prepared in Comparative Examples 1 and 2;

[0045] Figure 7 The graphs show the temperature variation over time of the high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber prepared in Test Example 1 of the present invention and the rubbers prepared in Comparative Examples 1 and 2. DETAILED DESCRIPTION

[0046] The present invention is described in detail below with reference to specific drawings and test examples. It is necessary to point out that the following test examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0047] Experimental materials:

[0048] Emulsion styrene butadiene rubber (ESBR): brand 1502, purchased from China National Petroleum Corporation.

[0049] Dicumyl peroxide (DCP): chemical formula is C 18 H 22 O2, M = 270.37 g / mol, purity 99%, purchased from Aladdin Reagent Co., Ltd.

[0050] Silicon dioxide (SiO2) with a purity of 99% was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0051] Phenyl-1,4-diboronic acid (C6H8B2O4): M=165.75 g / mol, purity 97%, purchased from Aladdin Reagent Co., Ltd.

[0052] Anhydrous magnesium sulfate (MgSO4): purity 97%, purchased from Aladdin Reagent Co., Ltd.

[0053] 1-Thioglycerol (C3H8O2S): M=108.16 g / mol, purity 99%, purchased from Aladdin Reagent Co., Ltd.

[0054] Tetrahydrofuran (THF): 99% purity, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0055] Dichloromethane (DCM): Purity: 99%, purchased from Aladdin Reagent Co., Ltd.

[0056] Stearic acid (SA): purchased from Aladdin Reagent Co., Ltd.

[0057] Zinc oxide (ZnO): purchased from Aladdin Reagent Co., Ltd.

[0058] N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ): purchased from Aladdin Reagent Co., Ltd.

[0059] Diphenylguanidine (accelerator D): purchased from Aladdin Reagent Co., Ltd.

[0060] Antiaging agent: brand 4010NA, purchased from Aladdin Reagent Co., Ltd.

[0061] The parts in the Examples and Comparative Examples are parts by weight.

[0062] In the present invention, Phr (parts per hundreds of rubber) refers to the number of parts added per 100 parts by weight of rubber.

[0063] The parts in the Examples, Test Examples and Comparative Examples are parts by weight.

[0064] Example 1

[0065] S1: DCP (0.25 phr) and 100 phr SBR were blended in a two-roll mill, and the crosslinking agent and the rubber were fully mixed by cutting and triangular bagging to obtain a first blend; wherein the blending time was 10 min.

[0066] S2: After the first blend is left to stand for 8 hours, its curing time t is measured by a rotorless curing instrument. 90 .

[0067] S3: In a flat vulcanizing press, the first blend is subjected to compression vulcanization to obtain a vulcanized rubber sheet. The compression vulcanization temperature is 160°C, the pressure is 15 MPa, and the time is t 90 +3 minutes.

[0068] S4: Crushing the vulcanized rubber sheet in an open mill for 5 minutes to obtain a polymer-based filler MSPPs-0.25 with an average particle size of 2.1 μm, wherein 0.25 represents the content of DCP in the polymer-based filler.

[0069] S5: MSPPs-0.25 was further processed by a planetary ball mill. The size of the spherical graphite beads was 0.5 mm, the mass ratio of the spherical graphite beads to the material was 100:1, and the ball milling time was 3 h. The polymer-based filler PNPs-0.25 with an average particle size of 390 nm was obtained. 0.25 represents the DCP content in the polymer-based filler.

[0070] Example 2

[0071] This embodiment is basically the same as embodiment 1, with the only difference being that the amount of DCP added in step S1 is 0.5 phr, so that a polymer-based filler PNPs-0.5 with an average particle size of 390 nm is obtained.

[0072] Example 3

[0073] This embodiment is basically the same as embodiment 1, with the only difference being that the amount of DCP added in step S1 is 1.0 phr, so that a polymer-based filler PNPs-1.0 having an average particle size of 400 nm is obtained.

[0074] Test Example 1

[0075] S1: 1 phr DCP and 100 phr SBR were blended in a two-roll mill, and the crosslinker and the rubber were fully mixed by cutting and triangular bagging to obtain a first blend; wherein the blending time was 10 min.

[0076] S2: After the first blend is left to stand for 8 hours, its curing time t is measured by a rotorless curing instrument. 90 .

[0077] S3: In a flat vulcanizing press, the first blend is subjected to compression vulcanization to obtain a vulcanized rubber sheet. The compression vulcanization temperature is 160°C, the pressure is 15 MPa, and the time is t 90 +3 minutes.

[0078] S4: Crushing the vulcanized rubber sheet in an open mill for 5 minutes to obtain a polymer-based filler MSPPs-1.0 with an average particle size of 1 μm, where 1.0 represents the DCP content in the vulcanized rubber sheet.

[0079] S5: MSPPs-1.0 was further processed by a planetary ball mill with a 0.5 mm spherical graphite bead size and a 100:1 mass ratio of spherical graphite bead to material for 3 h to obtain a polymer-based filler PNPs-1.0, where 1.0 represents the DCP content in the polymer-based filler.

[0080] S6: 17 phr of PNPs-1.0 and 100 phr of ESBR were blended on a two-roll mill, and then 1 phr of SA, 5 phr of ZnO, 2 phr of antioxidant 4010NA, 1.6 phr of accelerator CZ, 2 phr of accelerator D and 1.5 phr of sulfur S were added in sequence to obtain a rubber compound; wherein the blending time was 10 min.

[0081] S7: After the rubber mix has been allowed to stand for 8 hours, the curing time t of the rubber mix is measured using a rotorless curing instrument. 90 .

[0082] S8: The mixed rubber is subjected to compression vulcanization at 150° C. and 15 MPa on a flat vulcanizer to obtain a high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber PNPs / ESBR-1.0.

[0083] Comparative Example 1

[0084] First, use an internal mixer to compound the rubber matrix with white carbon black. Set the mold cavity temperature of the internal mixer to 40°C and the rotor speed to 45rpm, add ESBR and plasticize for 2 minutes. Then add SA, ZnO and antioxidant 4010NA and mix them with ESBR for 2 minutes. After that, add silica to the internal mixer in batches within 6 minutes to obtain the first stage rubber mix. After the rubber compound cools to room temperature, use an open mill to add the vulcanization system (accelerator D, accelerator CZ and sulfur S) to the first stage rubber mix to obtain the final rubber mix. After the rubber compound is allowed to stand for 8 hours, the molding vulcanization time t of the rubber compound is tested by a vulcanizer. 90 Subsequently, the samples were compression-vulcanized at 150°C and 15 MPa using a flat-plate vulcanizing press. 90 +3 minutes for vulcanization; for samples tested for rolling resistance, three times (t 90 The prepared composite material was named Silica / ESBR.

[0085] Comparative Example 2

[0086] The preparation of the rubber compound with the coupling agent Si69 is divided into three stages: (1) The first stage is basically the same as the first stage of the Silica / ESBR rubber compound, except that the silica is first mixed with the coupling agent Si69 and then added to the internal mixer cavity in batches to obtain the first stage of the rubber compound; (2) The mold cavity temperature is raised to 150°C, and the first stage of the rubber compound is heat-treated for 5 minutes. The speed of the internal mixer rotor is controlled to maintain the mold cavity temperature at around 150°C. This stage allows the coupling agent and silica to fully react to obtain the second stage of the rubber compound. (3) The third stage is to add the vulcanization system, which is consistent with the steps of Silica / ESBR. The subsequent hot molding steps of samples with different test conditions are also consistent with the preparation of Silica / ESBR. The resulting composite material is named Silica-Si69 / ESBR.

[0087] The composite materials obtained in Test Example 1 and Comparative Examples 1-2 were tested for performance respectively; wherein, the PNPs / ESBR vulcanization time for rubber tensile test was t 90 +3 minutes, the curing time of PNPs / ESBR for rolling resistance test is three times (t 90 +3 minutes).

[0088] The polymer-based fillers prepared in Examples 1 to 3 were subjected to SEM testing and dynamic light scattering testing. The results are as follows: Figure 2 As shown. Figure 2 It can be seen that the polymer-based fillers prepared in Examples 1 to 3 are similar to spherical shapes, and the average particle size of the polymer-based fillers prepared in Examples 1 to 3 is in the range of 0.3 to 0.6 μm.

[0089] According to GB / T 528-2009, the tensile mechanical properties of the high strength, high toughness, low energy consumption and low heat generation rubber prepared in Test Example 1 and the rubber prepared in Comparative Examples 1 and 2 were tested. Figure 3 The uniaxial tensile stress-strain curve is shown. Figure 3 It can be seen that for the system (Comparative Example 1) adding white carbon black, the tensile property of composite material reaches 25MPa, and elongation at break is about 800%.And the white carbon black system (Comparative Example 2) having added Si69, its tensile property is the most excellent, and tensile strength can reach 35MPa, and elongation at break is about 700%.This is mainly due to the addition of Si69 improving the dispersion of white carbon black in matrix, while improving the interaction intensity between white carbon black and matrix molecular chain, and then significantly improving the tensile property of composite material.And for the system (Test Example 1) adding polymer-based nano filler PNPs / ESBR-1.0 of the present invention, because the chemical structure identical with matrix of PNPs / ESBR-1.0 filler is close, so that the filler has better dispersibility in matrix.Meanwhile, the interface co-crosslinking between filler and matrix makes composite material show better synergistic effect in stretching process, and the tensile property of Test Example 1 is substantially suitable with the tensile property of Comparative Example 1.

[0090] The uniaxial tensile stress-strain curves of the high-strength, high-toughness, low-energy-consumption, low-heat-generation rubber prepared in Test Example 1 and the rubber prepared in Comparative Examples 1 and 2 were integrated to obtain Figure 4 The toughness statistics comparison chart shown. Figure 4 As can be seen, Comparative Example 2 has the highest mechanical toughness, reaching about 82MJ / m 3 This is mainly due to the addition of Si69, which reduces the size of silica agglomerates and makes the nano-enhancement effect of silica more obvious. For Test Example 1, its mechanical toughness is slightly higher than that of Comparative Example 1, confirming that its toughening effect is basically equivalent to that of Comparative Example 1.

[0091] According to GB 1685-1985, the high strength, high toughness, low energy consumption and low heat generation rubber prepared in Test Example 1 and the rubber prepared in Comparative Examples 1 and 2 were tested for hysteresis loss performance. Figure 5The cyclic stretching-recovery curve shown in FIG2 is shown; wherein the cyclic stretching times are 1, 2, 3, 4, and 5 times respectively. Those skilled in the art know that during the cyclic stretching process, the area enclosed by the stretching curve and the recovery curve can qualitatively characterize the hysteresis loss performance of the composite material. Figure 5 It can be seen that for the system filled with white carbon black (Comparative Example 1), during the cyclic stretching process, its hysteresis loop area is larger, indicating that the hysteresis performance of the composite material is the worst. For the white carbon black system with Si69 added (Comparative Example 2), since the coupling agent reduces the degree of agglomeration of white carbon black, thereby reducing the energy loss caused by filler friction, and at the same time, the coupling agent improves the bonding strength between white carbon black and the matrix, reduces the friction loss between the filler and the matrix, and the hysteresis loss performance of the composite material is improved. As for the polymer-based nanofiller (Test Example 1), its excellent dispersion and good interfacial co-crosslinking reaction make the hysteresis loss of the composite material the lowest, with excellent low energy consumption performance.

[0092] The ratio of the integral area of the hysteresis loop enclosed by the cyclic stretch-recovery curve of Test Example 1 to the integral area of the cyclic stretch-recovery curve of Test Example 1 is the hysteresis energy loss percentage of Test Example 1. The hysteresis energy loss percentages of Comparative Examples 1 and 2 are also calculated according to the above method, and the final result is Figure 6 The following is a schematic diagram of the hysteresis energy loss percentages for Test Example 1 and Comparative Examples 1-2 (a total of 5 cycles). Compared to Comparative Example 1, the hysteresis energy loss for Test Example 1 was reduced by 25%-30%, while compared to Comparative Example 2, the hysteresis energy loss for Test Example 1 was reduced by 15%-20%. This further demonstrates the excellent low energy consumption performance of the present invention.

[0093] Rolling resistance tests were conducted on the high-strength, high-toughness, low-energy consumption, and low-heat generation rubber prepared in Test Example 1, and the rubbers prepared in Comparative Examples 1 and 2. The specific testing method was as follows: A rubber rolling resistance tester (Model: RSS-II) was used to test the dynamic properties of the composite materials. The prepared specimens were solid tire models with an outer diameter of 10.2 cm, an inner diameter of 6.35 cm, and a thickness of 1.90 cm. During the test, a load of 30 kg was applied to the sample, the sample rotation speed was 400 rpm, and the test duration was 30 minutes. The temperature rise of the test sample over time was recorded.

[0094] Figure 7 The temperature variation curves of the high strength, high toughness, low energy consumption and low heat generation rubber prepared in Test Example 1 and the rubber prepared in Comparative Examples 1 and 2 during the rolling force test are shown. Figure 7As can be seen, the dynamic heat generation of Comparative Example 1 increased from 25°C to 72.3°C as the test time increased, a temperature increase of 47°C. In Comparative Example 2, in which Si69 was added, the temperature of the composite material increased by 41°C as the test time increased. In Test Example 1, which was filled with the polymer-based nanofiller of the present invention, the temperature of the composite material only increased by 36°C. Therefore, the PNPs / ESBR-1.0 prepared with the polymer-based nanofiller of the present invention has a significant advantage in improving the dynamic heat generation performance of the composite material.

Claims

1. A method for preparing high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber, characterized by: The preparation method comprises the following steps S1: blending the thermosetting rubber and the vulcanizing agent to obtain a first blend; S2: The first blend is allowed to stand, and the curing time t of the first blend is measured. 90 ; S3: performing compression vulcanization on the first blend to obtain a vulcanized rubber sheet; S4: crushing the vulcanized rubber sheet to obtain a polymer-based filler with an average particle size of 1 to 2.5 μm; S5: ball milling the polymer-based filler having an average particle size of 1 to 2.5 μm to obtain a polymer-based filler having an average particle size of 0.3 to 0.6 μm; S6: blending the polymer-based filler having an average particle size of 0.3 to 0.6 μm with the emulsion-polymerized thermosetting rubber; sequentially adding a first vulcanization accelerator, an activator, an antioxidant, a second vulcanization accelerator, a third vulcanization accelerator, and a vulcanizing agent to obtain a rubber mixture; S7: The rubber mix is allowed to stand and the curing time t of the rubber mix is measured. 90 ; S8: The mixed rubber is subjected to molding and vulcanization to obtain a high-strength, high-toughness, low-energy consumption and low-heat generation rubber.

2. The preparation method according to claim 1, wherein: In step S1, The thermosetting rubber is any one of styrene-butadiene rubber, natural rubber, and EPDM rubber; and / or The vulcanizing agent is any one of dicumyl peroxide and sulfur; and / or The weight ratio of the thermosetting rubber to the vulcanizing agent is 100:0.2-2.0, preferably 100:0.25-1.0; and / or The blending time is 10 to 20 minutes, preferably 10 to 15 minutes; and / or The blending method is the knife method and / or the triangle bag method.

3. The preparation method according to claim 1, wherein: In step S2, The standing time is 6 to 24 hours, preferably 8 to 12 hours.

4. The preparation method according to claim 1, wherein: In step S3, The temperature of the mold vulcanization is 150-170°C, preferably 160-165°C; and / or The pressure of the mold vulcanization is 10 to 15 MPa, preferably 13 to 15 MPa; and / or The time of molding vulcanization is t 90 +3 minutes~t 90 +5 minutes, preferably t 90 +3 minutes~t 90 +4 minutes.

5. The preparation method according to claim 1, wherein: In step S4, The crushing time is 5 to 20 minutes, preferably 5 to 15 minutes.

6. The preparation method according to claim 1, wherein: In step S5, The ball milling time is 3 to 5 hours, preferably 3 to 4 hours; Preferably, Ball milling treatment uses a star ball mill; More preferably, The size of the spherical graphite beads in the planetary ball mill is 0.5 to 2.0 mm; and / or The mass ratio of the spherical graphite beads in the planetary ball mill to the polymer-based filler with an average particle size of 0.3 to 0.6 μm is 100 to 200:

1.

7. The preparation method according to claim 1, wherein: In step S6, The first vulcanization accelerator is any one of stearic acid, sodium stearate, and potassium stearate; and / or The activator is any one of zinc oxide, potassium disulfide, and benzoyl peroxide; and / or The second vulcanization accelerator is any one of N-cyclohexyl-2-benzothiazole sulfenamide and dibenzothiazyl disulfide; and / or The third vulcanization accelerator is any one of diphenylguanidine and tetramethylthiuram disulfide; and / or The vulcanizing agent is sulfur; and / or The weight ratio of the emulsion-polymerized thermosetting rubber, the polymer-based filler having an average particle size of 0.3 to 0.6 μm, the first vulcanization accelerator, the activator, the antioxidant, the second vulcanization accelerator, the third vulcanization accelerator, and the vulcanizing agent is 100:10 to 17:0.8 to 1.2:4 to 6:0.8 to 2.0:1.2 to 1.8:1.8 to 2.2:1.0 to 1.6; and / or The blending time is 10 to 15 minutes; and / or The blending method is the knife method and / or the triangle bag method.

8. The preparation method according to claim 1, wherein: In step S7, The standing time is 6 to 24 hours, preferably 8 to 12 hours.

9. The preparation method according to claim 1, wherein: In step S8, The temperature of the mold vulcanization is 143 to 155°C, preferably 150 to 155°C; and / or The pressure of the mold vulcanization is 10 to 15 MPa, preferably 13 to 15 MPa; and / or The time of molding vulcanization is t 90 +3 minutes~t 90 +5 minutes, preferably t 90 +3 minutes~t 90 +4 minutes.

10. A high-strength, high-toughness, low-energy-consumption, and low-heat-generation rubber obtained by the preparation method according to any one of claims 1 to 9.

Images