Preparation method of polymer-based filler, polymer-based filler, preparation method of rubber composite material and rubber composite material

Abstract

The invention relates to a preparation method of a polymer-based filler, the polymer-based filler, a preparation method of a rubber composite material and the rubber composite material. The preparation method of the polymer-based filler comprises the following steps: blending thermosetting rubber and a vulcanizing agent to obtain a first blend; standing the first blend, and measuring the positive vulcanization time t90 of the first blend; carrying out mold pressing vulcanization on the first blend to obtain a vulcanized rubber sheet; and crushing the vulcanized rubber sheet to obtain the polymer-based filler with an average particle size of 1-2.5 [mu] m. According to the polymer-based filler prepared by the preparation method of the polymer-based filler, on one hand, the polymer-based filler has good compatibility with a rubber matrix, is not easy to form aggregates, and has excellent dispersion performance; and on the other hand, the interface bonding strength with a rubber matrix is higher. And the rubber composite material which is prepared by taking the polyisoprene rubber as a rubber reinforcing filler has high strength, high toughness, low hysteresis and excellent dynamic performance.

Description

Technical Field

[0001] The present invention relates to the field of filler technology, and more particularly, to a method for preparing a polymer-based filler, and the polymer-based filler obtained by the preparation method. Furthermore, the present invention relates to a method for preparing a rubber composite material, and the rubber composite material obtained by the preparation method. Background Art

[0002] Due to its unique entropic elasticity, rubber materials can deform by 100% to 2000% under low stress (0.1 to 20 MPa). Furthermore, they can quickly recover after stress removal, with a recovery rate of 80% to 100%. This unique property makes rubber materials irreplaceable and important in many fields, including tires, sealants, shock absorbers, robotics, artificial prostheses, and muscles. However, the low modulus, tensile stress, tear strength, and wear resistance of pure rubber materials make them unable to meet the strength requirements of engineering applications. Given that the mechanical strength and toughness of pure rubber materials often fail to meet actual engineering requirements, many rubber reinforcement methods have been explored. Among them, the longest-standing and most widely used strategy is the filled rubber reinforcement strategy. For example, compounding rubber materials with nanoparticles such as carbon black, silica, graphene, and carbon nanotubes is the most commonly used reinforcement method.

[0003] Although the introduction of these nanoparticles can greatly improve the mechanical strength, mechanical toughness, tear resistance, fatigue resistance, etc. of rubber materials. However, due to the poor compatibility of the aforementioned nanofillers with the rubber matrix, the fillers are prone to aggregation; and the filling-type reinforcement strategy often significantly increases the complexity of the internal interactions of rubber composites. The friction between fillers and between fillers and matrix polymer chains leads to the deterioration of the viscoelasticity of the composite material, increased hysteresis loss, a large amount of dynamic heat generation, and a decrease in dynamic performance, causing it to dissipate more energy under dynamic conditions. Taking carbon black as an example, the strong van der Waals force makes it very easy for carbon black to form agglomerates in the rubber matrix (such as Figure 1 ); Furthermore, the significant difference in surface energy between carbon black and rubber results in poor compatibility between the two, leading to poor dispersion within the rubber matrix. Therefore, balancing the reinforcement, toughening, and dynamic properties of filled rubber composites is crucial.

[0004] Researchers are committed to the functionalization modification of rubber materials, the functionalization of fillers, and the development of coupling agents to improve the compatibility of rubber with traditional fillers, thereby improving the dynamic and static mechanical properties of composite materials. For example, Xu et al. prepared styrene-butadiene rubber grafted with hydroxyethyl acrylate (SBR-g-HEA). The hydroxyl groups on the grafted unit HEA can form hydrogen bonds with the silanol groups on the surface of silica (such as Figure 2); Compared with the composite material with the addition of TESPT, SBR-g-HEA significantly enhanced the interfacial interaction between silica and rubber, and thus the SBR-g-HEA composite material exhibited excellent static and dynamic mechanical properties; more importantly, the performance of the composite material can be adjusted by precisely controlling the grafting rate of HEA according to actual usage requirements. The flexibility of this method has significant advantages in dealing with different application scenarios.

[0005] The development of coupling agents is an important method to improve the dispersion of fillers and enhance the bonding strength between fillers and matrix. Guo et al. synthesized an imine compound (DADI) containing an adamantane structure as a coupling agent (e.g. Figure 3 DADI acts as a bridge, transferring radicals from the matrix chains to the carbon black surface, establishing covalent bonds between the matrix and particles. This improves interfacial interactions and the dispersion of carbon black particles, reducing the dynamic heat generation and power loss of the composite. Wang et al. successfully grafted a copolymer of sulfur and styrene onto the carbon black surface through an inverse vulcanization reaction, significantly improving the dispersion of particles in the matrix and the interfacial bonding strength. This, in turn, improved the rolling resistance and dynamic heat generation of the composite.

[0006] While the aforementioned technical solutions address the dispersibility of traditional fillers and the interfacial bonding strength between traditional fillers and the matrix, thereby achieving a balance between strength, toughness, and dynamic performance in composite materials, they all involve complex chemical synthesis and preparation processes. Consequently, developing a new filler that can improve the overall performance of composite materials without requiring complex chemical synthesis and preparation processes has become a pressing challenge for those skilled in the art. Summary of the Invention

[0007] To solve the problems existing in the prior art, the present invention provides a method for preparing a polymer-based filler, which takes reducing the particle size of the filler, improving the dispersibility of the filler, and enhancing the interfacial bonding strength between the filler and the rubber matrix as the starting point. The polymer-based particles prepared by a simple, fast and large-scale application preparation method are used as reinforcing fillers. The rubber composite material reinforced with the polymer-based filler has high strength, high toughness, low hysteresis and excellent dynamic performance.

[0008] One of the purposes of the present invention is to provide a method for preparing a polymer-based filler, the method comprising the following steps:

[0009] S1: blending the thermosetting rubber and the vulcanizing agent to obtain a first blend;

[0010] S2: The first blend is allowed to stand, and the curing time t of the first blend is measured. 90 ;

[0011] S3: performing compression vulcanization on the first blend to obtain a vulcanized rubber sheet;

[0012] S4: The vulcanized rubber sheet is crushed to obtain a polymer-based filler with an average particle size of 1 to 2.5 μm.

[0013] The preparation method may specifically include:

[0014] 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.

[0015] 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 .

[0016] S3: performing compression vulcanization on the first blend using a flat vulcanizing press to obtain a vulcanized rubber sheet.

[0017] 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.

[0018] 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 cutting knife method and / or a triangle bag method.

[0019] 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.

[0020] In a preferred embodiment of the present invention, in step S2, the standing time is 6 to 24 hours, preferably 8 to 12 hours.

[0021] In a preferred embodiment of the present invention, in step S3,

[0022] The temperature of the mold vulcanization is 150-170°C, preferably 160-165°C; and / or

[0023] The pressure of the mold vulcanization is 10 to 15 MPa, preferably 13 to 15 MPa; and / or

[0024] The time of molding vulcanization is t 90 +3 minutes~t 90 +5 minutes, preferably t 90 +3 minutes.

[0025] In a preferred embodiment of the present invention, in step S4, the crushing time is 5 to 20 minutes, preferably 5 to 15 minutes.

[0026] In a preferred embodiment of the present invention, the preparation method further comprises the following steps:

[0027] 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.

[0028] In a preferred embodiment of the present invention, in step S5,

[0029] The ball milling time is 3 to 5 hours, preferably 3 to 4 hours;

[0030] Preferably,

[0031] Ball milling treatment uses a star ball mill;

[0032] More preferably,

[0033] The size of the spherical graphite beads in the planetary ball mill is 0.5 to 2.0 mm; and / or

[0034] The mass ratio of the spherical graphite beads to the polymer-based filler with an average particle size of 1 to 2.5 μm in the planetary ball mill is 100 to 200:1.

[0035] The second object of the present invention is to provide a polymer-based filler prepared by the preparation method of the first object of the present invention.

[0036] The third object of the present invention is to provide a method for preparing a rubber composite material containing the second object of the present invention, the polymer-based filler, the preparation method comprising the following steps:

[0037] (1) taking the polymer-based filler prepared by the preparation method described in the first object of the present invention or the polymer-based filler described in the second object of the present invention, blending it with styrene-butadiene rubber; adding a crosslinking agent, and blending to obtain a rubber compound;

[0038] (2) The rubber mix is allowed to stand and the curing time t of the rubber mix is measured. 90 ;

[0039] (3) the rubber mix is subjected to molding vulcanization to obtain a rubber composite material;

[0040] The preparation method may specifically include:

[0041] (1) A polymer-based filler prepared by the preparation method described in one of the objectives of the present invention or a polymer-based filler described in the second objective of the present invention is mixed with a certain amount of styrene-butadiene rubber on a two-roll mill; a cross-linking agent is then added to fully mix the components to obtain a rubber compound.

[0042] (2) After the rubber mix is left to stand for a certain period of time, the curing time t of the rubber mix is measured by a rotorless curing instrument. 90 .

[0043] (3) The mixed rubber is molded and vulcanized using a flat vulcanizer to obtain a smooth and flat rubber composite material.

[0044] In a preferred embodiment of the present invention,

[0045] In step (1), the weight ratio of the styrene-butadiene rubber, the polymer-based filler, and the cross-linking agent is 100:10-65:2-5; and / or the cross-linking agent is any one of sulfur, dicumyl peroxide, and 2,2-(1,4-phenylene)-bis[4-mercapto-1,3,2-dioxaborane]; and / or the blending time is 10-20 minutes; and / or the blending method is a cutting knife method and / or a triangle bagging method; and / or

[0046] In step (2), the standing time is 6 to 24 hours, preferably 8 to 12 hours; and / or

[0047] In step (3), the temperature of the compression vulcanization is 155-165°C; and / or the pressure of the compression vulcanization is 13-15 MPa; and / or the time of the compression vulcanization is t 90 +3 minutes~t 90 +5 minutes.

[0048] The fourth object of the present invention is to provide a rubber composite material obtained by the preparation method of the third object of the present invention.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] 1. The polymer-based filler prepared by the preparation method of the polymer-based filler in the present invention has good compatibility with the rubber matrix, is not easy to form agglomerates, and has excellent dispersion performance; on the other hand, it has high interface bonding strength with the rubber matrix.

[0051] 2. The preparation method of the polymer-based filler in the present invention is simple and quick, does not involve complicated chemical synthesis and preparation processes, and is suitable for large-scale application.

[0052] 3. The polymer-based filler prepared by the present invention has surface chemical activity, and its modulus and size are adjustable.

[0053] 4. The polymer-based filler prepared by the preparation method of the polymer-based filler of the present invention is used as a rubber reinforcing filler, and the obtained rubber composite material has high strength, high toughness, low hysteresis and excellent dynamic performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 Schematic diagram of carbon black forming agglomerates in a rubber matrix in the prior art;

[0055] Figure 2 Schematic diagram of the mechanism of interaction between silica and rubber molecular chains in the composite material in the prior art;

[0056] Figure 3 Schematic diagram of the mechanism of action of the interface coupling agent between carbon black and natural rubber in the composite material in the prior art;

[0057] Figure 4 Schematic diagram of the preparation process of the low-energy-consumption and high-mechanical-strength rubber composite material of the present invention;

[0058] Figure 5 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;

[0059] Figure 6 The SEM images and particle size distribution diagrams of the polymer-based fillers prepared in Examples 4 to 6 of the present invention are shown;

[0060] Figure 7 This is a sedimentation experiment of the polymer-based fillers prepared in Examples 3 and 6 of the present invention;

[0061] Figure 8 TEM images of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 7 and 19 of the present invention and the rubber composite material prepared in Comparative Example 3;

[0062] Figure 9 The tensile stress-strain curves of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 1 to 20 of the present invention and the rubber composite materials prepared in Comparative Examples 1 to 8;

[0063] Figure 10 Statistical comparison of tensile strength and elongation at break of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 1 to 20 of the present invention and the rubber composite materials prepared in Comparative Examples 5 to 8;

[0064] Figure 11 The stretch-recovery curves of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 1 to 20 of the present invention and the rubber composite materials prepared in Comparative Examples 5 to 8;

[0065] Figure 12 Young's modulus graphs and modulus-displacement curves of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 11, 15, and 19 of the present invention and the rubber composite material prepared in Comparative Example 7;

[0066] Figure 13 Cyclic stretch-recovery curves of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 11-12, 15-16, and 19-20 of the present invention and the rubber composite materials prepared in Comparative Examples 3-4 and 7-8;

[0067] Figure 14 Statistical comparison of hysteresis energy loss of the low-energy-consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 9 to 20 of the present invention and the rubber composite materials prepared in Comparative Examples 1 to 8;

[0068] Figure 15 The power loss curves of the low-energy-consumption and high-mechanical-strength rubber composite material prepared in Experimental Example 19 and the rubber composite materials prepared in Comparative Examples 3 and 7 are plotted over time. DETAILED DESCRIPTION

[0069] The present invention will be described in detail below with reference to specific drawings and embodiments. It is necessary to point out that the following embodiments 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.

[0070] Experimental materials:

[0071] Solution styrene butadiene rubber (SBR): brand 2466, purchased from Taiwan Rubber Corporation.

[0072] Dicumyl peroxide (DCP): chemical formula is C 18 H 22 O2, M = 270.37 g / mol, purity 99%, purchased from Aladdin Reagent Co., Ltd.

[0073] Silicon dioxide (SiO2) with a purity of 99% was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0074] Phenyl-1,4-diboronic acid (C6H8B2O4): M=165.75 g / mol, purity 97%, purchased from Aladdin Reagent Co., Ltd.

[0075] Anhydrous magnesium sulfate (MgSO4): purity 97%, purchased from Aladdin Reagent Co., Ltd.

[0076] 1-Thioglycerol (C3H8O2S): M=108.16 g / mol, purity 99%, purchased from Aladdin Reagent Co., Ltd.

[0077] Tetrahydrofuran (THF): 99% purity, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0078] Dichloromethane (DCM): Purity: 99%, purchased from Aladdin Reagent Co., Ltd.

[0079] The parts in the Examples, Test Examples and Comparative Examples are parts by weight.

[0080] In the present invention, Phr (parts per hundreds of rubber) refers to the number of parts added per 100 parts by weight of rubber.

[0081] Example 1

[0082] 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.

[0083] S2: After the first blend is left to stand for 8 hours, its curing time t is measured by a rotorless curing instrument. 90 .

[0084] 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.

[0085] 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.

[0086] Example 2

[0087] 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 MSPPs-0.5 with an average particle size of 2.0 μm is obtained.

[0088] Example 3

[0089] This embodiment is substantially the same as embodiment 1, with the only difference being that the amount of DCP added in step S1 is 1.0 phr, thereby obtaining a polymer-based filler MSPPs-1.0 having an average particle size of 1.2 μm.

[0090] Example 4

[0091] 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.

[0092] S2: After the first blend is left to stand for 8 hours, its curing time t is measured by a rotorless curing instrument. 90 .

[0093] 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.

[0094] 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.

[0095] 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.

[0096] Example 5

[0097] This embodiment is basically the same as embodiment 4, with the only difference being that the amount of DCP added in step S1 is 0.5 phr, so a polymer-based filler PNPs-0.5 with an average particle size of 390 nm is obtained.

[0098] Example 6

[0099] This embodiment is basically the same as embodiment 4, 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 with an average particle size of 400 nm is obtained.

[0100] Test Example 1

[0101] (1) 11 phr of MSPPs-0.5 prepared in Example 2 was blended with 100 phr of SBR on a two-roll mill for 10 minutes; 2 phr of crosslinker BDB was added thereto, and the components were fully mixed by cutting and triangular bagging to obtain a rubber compound.

[0102] (2) 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 .

[0103] (3) The mixed rubber was vulcanized by molding in a flat vulcanizing press to obtain a smooth and flat vulcanized rubber sample SBR / MSPPs-0.5-10wt%; wherein the molding vulcanization temperature was 160°C, the pressure was 15 MPa, and the time was t 90 +3 minutes.

[0104] The process of preparing the rubber composite material using the polymer-based filler of the present invention is as follows: Figure 4 shown.

[0105] Test Example 2

[0106] This test example is basically the same as Test Example 1, except that 25 phr of the MSPPs-0.5 prepared in Example 2 was used in step (1), and a smooth and flat vulcanized rubber sample SBR / MSPPs-0.5-20 wt% was finally obtained.

[0107] Test Example 3

[0108] This test example is basically the same as Test Example 1, except that 43 phr of the MSPPs-0.5 prepared in Example 2 was used in step (1), and a smooth and flat vulcanized rubber sample SBR / MSPPs-0.5-30 wt% was finally obtained.

[0109] Test Example 4

[0110] This test example is basically the same as Test Example 1, except that 63 phr of the MSPPs-0.5 prepared in Example 2 was used in step (1), and a smooth and flat vulcanized rubber sample SBR / MSPPs-0.5-40 wt% was finally obtained.

[0111] Test Example 5

[0112] This test example is basically the same as Test Example 1, except that: in step (1), 11 phr of MSPPs-1.0 prepared in Example 3 was used to finally obtain a smooth and flat vulcanized rubber sample SBR / MSPPs-1.0-10 wt%.

[0113] Test Example 6

[0114] This test example is basically the same as Test Example 5, with the only difference being that 25 phr of the MSPPs-1.0 prepared in Example 3 was used in step (1), ultimately obtaining a smooth and flat vulcanized rubber sample SBR / MSPPs-1.0-20 wt%.

[0115] Test Example 7

[0116] This test example is basically the same as Test Example 5, with the only difference being that in step (1), 43 phr of the MSPPs-1.0 prepared in Example 3 was used to finally obtain a smooth and flat vulcanized rubber sample SBR / MSPPs-1.0-30 wt%.

[0117] Test Example 8

[0118] This test example is basically the same as Test Example 5, with the only difference being that in step (1), 63 phr of the MSPPs-1.0 prepared in Example 3 was used to finally obtain a smooth and flat vulcanized rubber sample SBR / MSPPs-1.0-40 wt%.

[0119] Test Example 9

[0120] This test example is essentially the same as Test Example 1, except that 11 phr of PNPs-0.25 prepared in Example 4 was used in step (1), ultimately yielding a smooth and level vulcanized rubber sample SBR / PNPs-0.25-10 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.25-10 vol % was obtained in Test Example 9.

[0121] Test Example 10

[0122] This test example is essentially the same as Test Example 9, except that 25 phr of PNPs-0.25 prepared in Example 4 was used in step (1), ultimately yielding a smooth and level vulcanized rubber sample SBR / PNPs-0.25-20 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.25-20 vol % was obtained in Test Example 10.

[0123] Test Example 11

[0124] This test example is essentially the same as Test Example 9, except that 43 phr of PNPs-0.25 prepared in Example 4 was used in step (1), ultimately yielding a smooth and level vulcanized rubber sample SBR / PNPs-0.25-30 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.25-30 vol % was obtained in Test Example 11.

[0125] Test Example 12

[0126] This test example is essentially the same as Test Example 9, except that 63 phr of PNPs-0.25 prepared in Example 4 was used in step (1) to obtain a smooth and level vulcanized rubber sample SBR / PNPs-0.25-40 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.25-40 vol % was obtained in Test Example 12.

[0127] Test Example 13

[0128] This test example is essentially the same as Test Example 1, except that 11 phr of PNPs-0.5 prepared in Example 5 was used in step (1), ultimately yielding a smooth and level vulcanized rubber sample SBR / PNPs-0.5-10 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.5-10 vol % was obtained in Test Example 13.

[0129] Test Example 14

[0130] This test example is essentially the same as Test Example 13, except that 25 phr of PNPs-0.5 prepared in Example 5 was used in step (1), ultimately yielding a smooth and level vulcanized rubber sample SBR / PNPs-0.5-20 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.5-20 vol % was obtained in Test Example 14.

[0131] Test Example 15

[0132] This test example is essentially the same as Test Example 13, except that 43 phr of PNPs-0.5 prepared in Example 5 was used in step (1) to obtain a smooth and level vulcanized rubber sample SBR / PNPs-0.5-30 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.5-30 vol % was obtained in Test Example 15.

[0133] Test Example 16

[0134] This test example is essentially the same as Test Example 13, except that 63 phr of PNPs-0.5 prepared in Example 5 was used in step (1) to obtain a smooth and level vulcanized rubber sample SBR / PNPs-0.5-40 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-0.5-40 vol % was obtained in Test Example 16.

[0135] Test Example 17

[0136] This test example is essentially the same as Test Example 1, except that 11 phr of PNPs-1.0 prepared in Example 6 was used in step (1), ultimately yielding a smooth and level vulcanized rubber sample, SBR / PNPs-1.0-10 wt %. It should be noted that a smooth and level vulcanized rubber sample, SBR / PNPs-1.0-10 vol %, was obtained in Test Example 17.

[0137] Test Example 18

[0138] This test example is essentially the same as Test Example 17, except that 25 phr of PNPs-1.0 prepared in Example 6 was used in step (1) to obtain a smooth and level vulcanized rubber sample SBR / PNPs-1.0-20 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-1.0-20 vol % was obtained in Test Example 18.

[0139] Test Example 19

[0140] This test example is essentially the same as Test Example 17, except that 43 phr of PNPs-1.0 prepared in Example 6 was used in step (1) to obtain a smooth and level vulcanized rubber sample SBR / PNPs-1.0-30 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-1.0-30 vol % was obtained in Test Example 19.

[0141] Test Example 20

[0142] This test example is essentially the same as Test Example 17, except that 63 phr of PNPs-1.0 prepared in Example 6 was used in step (1) to obtain a smooth and level vulcanized rubber sample SBR / PNPs-1.0-40 wt %. It should be noted that a smooth and level vulcanized rubber sample SBR / PNPs-1.0-40 vol % was obtained in Test Example 20.

[0143] Comparative Example 1

[0144] This comparative example is essentially the same as Experimental Example 1, except that 11 phr of SiO2 was added in step (1), resulting in a vulcanized rubber sample SBR / SiO2-w-10%. The average particle size of the SiO2 was 300 nm, and the SiO2-w-10% ratio meant that the mass of the SiO2 added was 10% of the mass of the SBR.

[0145] Comparative Example 2

[0146] This comparative example is basically the same as comparative example 1, except that 25 phr of SiO2 is added in step (1), and a vulcanized rubber sample SBR / SiO2-w-20% is finally obtained.

[0147] Comparative Example 3

[0148] This comparative example is basically the same as comparative example 1, except that 43 phr of SiO2 is added in step (1), and a vulcanized rubber sample SBR / SiO2-w-30% is finally obtained.

[0149] Comparative Example 4

[0150] This comparative example is basically the same as comparative example 1, except that 63 phr of SiO2 is added in step (1), and a vulcanized rubber sample SBR / SiO2-w-40% is finally obtained.

[0151] Comparative Example 5

[0152] This comparative example is essentially the same as Experimental Example 1, except that 27 phr of SiO2 was added in step (1), resulting in a vulcanized rubber sample SBR / SiO2-v-10%. The average particle size of the SiO2 is 300 nm, and the SiO2-v-10% composition means that the volume of the SiO2 filled is 10% of the volume of the SBR.

[0153] Comparative Example 6

[0154] This comparative example is basically the same as comparative example 5, except that 62 phr of SiO2 is added in step (1), and a vulcanized rubber sample SBR / SiO2-v-20% is finally obtained.

[0155] Comparative Example 7

[0156] This comparative example is basically the same as comparative example 1, except that 101 phr of SiO2 is added in step (1), and a vulcanized rubber sample SBR / SiO2-v-30% is finally obtained.

[0157] Comparative Example 8

[0158] This comparative example is basically the same as comparative example 1, except that 156 phr of SiO2 is added in step (1), and a vulcanized rubber sample SBR / SiO2-v-40% is finally obtained.

[0159] 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 5 As shown. Figure 5 It can be seen that the average particle size of the polymer-based fillers prepared in Examples 1 to 3 is in the range of 1 to 2.5 μm. The polymer-based fillers prepared in Examples 4 to 6 were subjected to SEM testing and dynamic light scattering testing. The results are as follows: Figure 6 As shown. Figure 6 It can be seen that the polymer-based fillers prepared in Examples 4 to 6 are similar to spherical shapes, and the average particle size of the polymer-based fillers prepared in Examples 4 to 6 is in the range of 0.3 to 0.6 μm.

[0160] The sedimentation test was conducted on the polymer-based filler MSPPs-1.0 prepared in Example 3 and the polymer-based filler PNPs-1.0 prepared in Example 6. The results are as follows: Figure 7 As shown. Figure 7 It can be seen that the polymer-based filler of the present invention has excellent dispersibility.

[0161] TEM tests were performed on the low energy consumption and high mechanical strength rubber composite materials obtained in Test Examples 7 and 19 and the rubber composite material obtained in Comparative Example 3. The results are as follows: Figure 8 As shown. Figure 8 It can be seen that the polymer-based fillers of the present invention have excellent dispersion properties in the rubber matrix. The TEM image of Comparative Example 3 shows severe SiO2 agglomeration, which is due to the poor affinity of the inorganic filler with the rubber matrix. However, the polymer-based fillers of Test Examples 7 and 19 have similar chemical structures to the rubber matrix, resulting in excellent affinity and uniform dispersion in the rubber matrix, which has a significant positive impact on the mechanical properties of the composite material.

[0162] According to GB / T 528-2009, the low energy consumption and high mechanical strength rubber composite materials prepared in Test Examples 1 to 20 and the rubber composite materials prepared in Comparative Examples 1 to 8 were subjected to tensile mechanical property tests, and the results were as follows: Figure 9 The tensile stress-strain curves are shown. It should be noted that when the filler mass fraction or filler volume fraction is 10%, 20%, 30%, or 40%, the tensile stress-strain curves of some test examples or comparative examples are similar, making them difficult to distinguish. Therefore, to facilitate differentiation, two separate graphs are provided for each filler mass fraction or filler volume.

[0163] By comparison Figure 9 Using data from the , the tensile mechanical properties of the composite material were analyzed based on filler size, filler dispersion, and filler-matrix compatibility. Compared to traditional inorganic SiO2, the polymer-based fillers of the present invention offer an advantage in their superior matrix compatibility. Furthermore, the chemical structure of the polymer-based fillers of the present invention allows for interfacial co-crosslinking reactions with the matrix.

[0164] by Figure 9(d) and 9 (h) are used as examples for illustration. Also at a filling fraction of 40wt%, the tensile strength of Comparative Example 4 (SBR / SiO2-w-40%) is only 5.9MPa, while the tensile strength of Test Example 20 (SBR / PNPs-1.0-40%) reaches 13MPa. Compared with traditional inorganic SiO2, the polymer-based filler of the present invention has a significant reinforcing effect on the rubber matrix. This is due to the presence of interfacial co-crosslinking, and PNPs has an effect of improving the strength of the composite material. Similarly, the elongation at break of Comparative Example 4 (SBR / SiO2-w-40%) is 250%, while the elongation at break of Test Example 20 (SBR / PNPs-1.0-40%) reaches 370%. This is due to the presence of interfacial co-crosslinking, and PNPs also has an effect of improving the elongation at break of the composite material.

[0165] Therefore, at the same filler fraction, the polymer-based filler of the present invention significantly improves the tensile mechanical properties of SBR. It should be noted that compared to MSPPs, PNPs have the advantage of particle size. PNPs have a low average particle size, reaching the nanometer scale. Therefore, the nano-enhancement effect of PNPs is more pronounced. At the same filler fraction, PNPs significantly outperform MSPPs in enhancing the SBR.

[0166] According to GB / T 528-2009, the tensile strength and elongation at break of the rubber composite materials with low energy consumption and high mechanical strength prepared in Test Examples 1 to 20 and the rubber composite materials prepared in Comparative Examples 5 to 8 were tested respectively, and the values were summarized to obtain Figure 10 The statistical comparison of tensile strength and elongation at break is shown in the figure. Figure 10 The effects of filler type and filler fraction on the tensile strength and elongation at break of the composites can be more clearly compared. The tensile strength and elongation at break of Test Examples 9 to 20 are both superior to those of Comparative Examples 5 to 8, demonstrating that the SBR / PNPs composites prepared using the PNPs of the present invention exhibit superior tensile mechanical properties.

[0167] According to GB 1685-1985, the low energy consumption and high mechanical strength rubber composite materials prepared in Test Examples 1 to 20 and the rubber composite materials prepared in Comparative Examples 5 to 8 were tested for hysteresis loss of the composite materials. Figure 11 The stretch-recovery curve shown. Those skilled in the art will appreciate that the area enclosed by the stretch curve and the recovery curve during cyclic stretching is defined as the hysteresis loss of the rubber material. A larger hysteresis loop area indicates a higher energy loss during dynamic loading. For Comparative Examples 5 to 8 (SiO2 systems), due to poor affinity between the filler and the matrix, aggregation between fillers, and poor dispersion of fillers, particularly the aggregation and poor affinity of the fillers, the composite material dissipated more energy during cyclic stretching.

[0168] And for test examples 9~20 (PNPs filler), because PNPs and matrix have similar chemical structure, so that PNPs dispersibility is improved in rubber matrix, the agglomeration of filler is reduced, and the friction energy dissipation between fillers is reduced during cyclic stretching. Meanwhile, the interfacial co-crosslinking reaction of PNPs and SBR reduces the friction loss at the interface during cyclic stretching. Under the above effect, the composite material filled with PNPs has a significantly reduced cyclic stretching hysteresis loop area, indicating that it has good low energy consumption performance. It can be seen from this that compared to SiO2 composite material system, the composite material system filled with PNPs has a lower hysteresis energy loss.

[0169] The low energy consumption and high mechanical strength rubber composite materials prepared in Experimental Examples 11, 15, and 19 and the rubber composite material prepared in Comparative Example 3 were tested using an atomic force microscope to obtain the following results: Figure 12 Young's modulus and modulus-displacement curves are shown. Figure 12 The Young's modulus diagram shows that the PNPs polymer-based filler of the present invention has better dispersion performance in the rubber matrix than the filler SiO2. Figure 12 The modulus-displacement curve shows that the interface bonding strength between the PNPs polymer-based filler and the rubber matrix is better than that of the filler SiO2.

[0170] According to GB 1685-1985, the low energy consumption and high mechanical strength rubber composite materials prepared in Test Examples 11-12, 15-16, 19-20 and the rubber composite materials prepared in Comparative Examples 3-4, 7-8 were subjected to cyclic tensile tests to obtain the following results: Figure 13 The cyclic stretch-recovery curve shown in the figure is 1. Figure 13 It can be seen that at the same filler filling fraction, the composite material system filled with PNPs of the present invention has lower hysteresis energy loss compared with the SiO2 composite material system.

[0171] According to GB 1685-1985, the low-energy consumption and high-mechanical-strength rubber composite materials prepared in Test Examples 9 to 20 and the rubber composite materials of Comparative Examples 1 to 8 were subjected to cyclic tensile tests. The hysteresis loops formed by the stretch-recovery curves of Test Examples 9 to 20 and Comparative Examples 1 to 8 were then integrated and calculated to obtain the corresponding hysteresis energy loss, and then the hysteresis energy loss was obtained. Figure 14 The statistical comparison diagram of hysteresis energy loss is shown. Those skilled in the art know that the size of the hysteresis loop is a qualitative comparison of the hysteresis loss performance of the composite material, while the size of the hysteresis loop area obtained by integration can be used to quantitatively compare the hysteresis energy loss of the composite material. Figure 14It can be seen that at a filler filling fraction of 30%, the hysteresis energy loss of the composite material system filled with PNPs of the present invention (Test Example 19) is reduced by 30.3% compared with the SiO2 composite material system; at a filler filling fraction of 40%, the hysteresis energy loss of the composite material system filled with PNPs of the present invention (Test Example 20) is reduced by 20.4% compared with the SiO2 composite material system, further confirming that the performance of the PNPs polymer-based filler of the present invention is outstanding.

[0172] The low-energy consumption and high-mechanical strength rubber composite material prepared in Test Example 19 and the rubber composite materials prepared in Comparative Examples 3 and 7 were subjected to rolling resistance tests. The specific test method is: using a rubber rolling resistance tester (model: RSS-II) to test the dynamic performance of the composite material. The prepared sample is a solid tire model 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, the load applied to the sample is 30 kg, the rotation speed of the sample is 400 rpm, and the test time is 30 minutes. The power loss curve of the test sample is recorded over time.

[0173] Figure 15 The graphs showing the power loss versus time of the low energy consumption and high mechanical strength rubber composite material prepared in Test Example 19 and the composite materials prepared in Comparative Examples 3 and 7 during the rolling force test are shown. Figure 15 It can be seen that the power loss of the composite material filled with PNPs (Test Example 19) during the rolling test was only 3.19 J / r, while the power loss of the SiO2 system filled with the same volume fraction (Comparative Example 7) reached 4.21 J / r. This confirms that the PNPs polymer-based filler of the present invention has a significant advantage in reducing the rolling resistance performance of the composite material and its elastic properties are more superior, which is consistent with the PNPs improving the hysteresis loss performance of the composite material.

Claims

1. A method for preparing a polymer-based filler, characterized in that: 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: The vulcanized rubber sheet is crushed to obtain a polymer-based filler with an average particle size of 1 to 2.5 μm.

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: The preparation method further comprises the following steps 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.

7. The preparation method according to claim 6, characterized in that: 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 1 to 2.5 μm is 100 to 200:

1.

8. A polymer-based filler obtained by the preparation method according to any one of claims 1 to 7.

9. A method for preparing a rubber composite material, characterized in that: Includes the following steps (1) taking the polymer-based filler prepared by the preparation method according to any one of claims 1 to 7 or the polymer-based filler according to claim 8, and blending it with styrene-butadiene rubber; adding a crosslinking agent, and blending to obtain a rubber compound; (2) The rubber mix is allowed to stand and the curing time t of the rubber mix is measured. 90 ; (3) the rubber mix is subjected to molding vulcanization to obtain a rubber composite material; Preferably, In step (1), the weight ratio of the styrene-butadiene rubber, the polymer-based filler, and the cross-linking agent is 100:10-65:2-5; and / or the cross-linking agent is any one of sulfur, dicumyl peroxide, and 2,2-(1,4-phenylene)-bis[4-mercapto-1,3,2-dioxaborane]; and / or the blending time is 10-20 minutes; and / or the blending method is a cutting knife method and / or a triangle bagging method; and / or In step (2), the standing time is 6 to 24 hours, preferably 8 to 12 hours; and / or In step (3), the temperature of the compression vulcanization is 155-165°C; and / or the pressure of the compression vulcanization is 13-15 MPa; and / or the time of the compression vulcanization is t 90 +3 minutes~t 90 +5 minutes.

10. A rubber composite material obtained by the preparation method according to claim 9.

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