Environment-friendly dual-active peptizing agent composition for rubber and preparation method and application thereof

Abstract

The present application relates to the rubber processing technical field, provide a kind of environment-friendly double active plasticizer composition and its rubber plasticing method.The composition is with 2,2'-dibenzoylaminodiphenyl disulfide as main active component, with small dose of pentachlorobenzene thiophenol, and adopts the double inorganic carrier formed by pottery and calcium carbonate, and phthalocyanine iron metal complex is loaded on the surface of carrier.Under the premise that zinc pentachlorothiophenol, zinc salt of fatty acid and other heavy metal salt activators are not contained, and the chlorine element content is controlled in the limited range, the plasticizer composition of the present application is used for the plasticing of raw rubber such as natural rubber, and the Mooney viscosity can be reduced faster at medium plasticing temperature, the plasticing time to reach target Mooney is significantly shortened, the unit energy consumption and motor load are reduced, and the equipment operation stability is improved.Comparative test proves that the composition has good formula freedom, has high-efficiency plasticing and environmental friendliness, and is suitable for tire and various rubber product production.

Description

Technical Field

[0001] This invention relates to the field of rubber processing technology, and in particular to an environmentally friendly dual-active plasticizer composition for rubber, its preparation method, and its application. Background Technology

[0002] In the rubber industry, natural rubber and some synthetic rubbers typically undergo plasticizing before entering subsequent processes such as mixing, calendering, extrusion, and molding. This process reduces the molecular chain length of the raw rubber, improves plasticity and flowability, and facilitates the uniform dispersion of subsequent compounding agents. For tires, hoses, belts, and other industrial rubber products, the plasticizing effect not only affects Mooney viscosity and processing window but also directly relates to subsequent mixing energy consumption, equipment load, dimensional stability of semi-finished products, and batch consistency of vulcanized products. Therefore, achieving stable, efficient, and environmentally friendly plasticizing at relatively mild process temperatures has always been a key technical challenge in the rubber processing field.

[0003] In existing plasticizing technologies, chemical plasticizers remain an important means of improving plasticizing efficiency. Traditional plasticizer systems can be broadly classified into two categories: one is the low-temperature active system represented by polychlorinated thiophenols and their metal salts, and the other is the high-temperature plasticizing system represented by aromatic disulfides. Among them, 2,2'-dibenzoylaminodiphenyl disulfide (DBD) is generally regarded as a typical high-temperature plasticizer due to its mature industrial application in rubber processing. At the same time, certain sulfur-containing heterocyclic compounds and metal macrocyclic complexes have also been proposed as synergistic plasticizing components in order to expand the effective temperature range of plasticizers and improve viscosity reduction efficiency.

[0004] For example, prior art document JP3602610B2 ​​discloses a technical solution for a non-caking plasticizer. This document explicitly states that DBD can be used as the active plasticizer component and can be combined with inert fillers to form granules or molded formulations, thereby improving feed metering, flowability, and dust control in the working environment. The document further indicates that optional inert fillers include kaolin, calcium carbonate, diatomaceous earth, and barium sulfate, among which kaolin and calcium carbonate are particularly suitable. Furthermore, the document discloses that the plasticizer, filler, and optional activator can all participate in granulation in fine powder form, with a particle size typically less than 200 μm, preferably even smaller, so that subsequent extrusion and granulation can form a free-flowing product that is not prone to clumping. Therefore, JP3602610B2 ​​demonstrates that by combining DBD with inorganic carriers such as kaolin and calcium carbonate, the problems of unstable feed, high dust levels, and easy clumping during storage of traditional powdered plasticizers can be solved to a certain extent.

[0005] However, the approach represented by JP3602610B2 ​​is essentially still centered on DBD, inert carriers, and molding processes. While this type of approach helps improve the physical form and ease of use of the plasticizer, its improvement on the plasticizing activity itself is limited, especially in the near-mid-temperature range (e.g., approximately 90–105°C). Relying solely on the DBD system often results in slow plasticizing onset, long time required to reach the target Mooney temperature, high unit energy consumption, and high motor load. In other words, existing DBD molding plasticizer approaches primarily address formulation and operability issues, while lacking more refined structural designs and clear synergistic technical solutions for further improving plasticizing efficiency in the mid-temperature range without relying on high-chlorine or heavy metal activation systems.

[0006] Another relevant prior art document, GB776101A, discloses the application of ferrophthalocyanine in rubber plasticization. This document indicates that natural rubber or styrene-butadiene rubber can be plasticized by introducing a small amount of ferrophthalocyanine or its substituted derivatives; furthermore, in its embodiments, ferrophthalocyanine can also be used in combination with various other sulfur-containing compounds, including pentachlorothiophenol and its zinc salt, thiol compounds, MBT (mercaptobenzothiazole), DBD, etc. This document actually illustrates an important technical idea: ferrophthalocyanine is not limited to being used alone as a plasticizing aid, but can be combined with various known plasticizers or synergistic components to improve the rate of rubber plasticization or improve the plasticization process. In other words, GB776101A has provided early technical inspiration for the synergistic approach of ferrophthalocyanine + sulfur-containing organic plasticizing components.

[0007] However, the main focus of GB776101A is to demonstrate the feasibility of using ferrophthalocyanine with different plasticizing components. Its approach leans more towards the possibility of component combinations, rather than addressing the more pressing environmental constraints, granule formulation design, and fine distribution structure of inorganic carriers in modern rubber industry. In particular, the scope of possible combinations in this document is broad, including MBT, DBD, and traditionally efficient but more environmentally burdensome components such as pentachlorothiophenol and its zinc salts. In other words, GB776101A provides a basic approach to possible combinations but fails to address the more practical question: after excluding halogenated thiophenols and zinc salt plasticizing activators, can ferrophthalocyanine still be used in combination with specific active components and specific inorganic carrier structures to achieve efficient viscosity reduction, low energy consumption, and low equipment load under medium-temperature plasticizing conditions?

[0008] As can be seen from the two existing technical documents mentioned above, the development of existing technologies has generally followed two paths: one path, represented by JP3602610B2, emphasizes the molding and low-dust production of DBD plasticizers, as well as the use of fillers such as kaolin and calcium carbonate to improve processing convenience; the other path, represented by GB776101A, emphasizes that ferrophthalocyanine can be used in combination with various organic sulfur-containing compounds such as MBT and DBD to enhance plasticizing effect. The former focuses more on carriers and formulations, while the latter focuses more on the combination of active systems. However, existing technologies have not yet fully answered the following question: if we want to avoid the use of halogenated thiophenols and their metal salts, and avoid the introduction of additional zinc salts or other heavy metal salt-type plasticizing activators, can we achieve a significant improvement in plasticizing efficiency in the mid-temperature range by relying solely on the synergy of the more environmentally friendly dual-active components and ferrophthalocyanine through specific loading methods, specific carrier ratios, and specific particle spatial distribution structures?

[0009] Furthermore, while inorganic fillers are frequently used as inert supports in existing technologies, their function is generally understood as dilution, bearing, improving flowability, or facilitating granulation. Existing literature typically lacks a detailed design regarding the functional division between different inorganic supports, such as one support preferentially loading catalytic components while another is used to regulate particle brittleness, dispersion pathways, and interfacial release behavior. Although JP3602610B2 ​​lists kaolin and calcium carbonate as suitable inert fillers, it does not provide more in-depth structural constraints regarding their sequential mixing relationships within the same particle, their proportion windows, or their impact on the release / dispersion behavior of the plasticizer. This results in existing molded plasticizers mostly remaining at the level of simple blended particles, lacking targeted control over the internal spatial distribution structure of the particles.

[0010] Similarly, for macrocyclic metal complexes like ferrophthalocyanine, GB 776101A has stated that they can participate in the plasticization process and synergistically interact with various organic plasticizing components. However, this document does not systematically explain which type of inorganic phase surface ferrophthalocyanine should be preferentially loaded onto, whether it should be located in the core or outer layer of the particle, and how its spatial relative position with the main active plasticizer and synergistic plasticizer in the particle affects plasticization efficiency. For modern continuous and automated rubber processing production lines, these factors precisely affect the initial wetting, dispersion rate, local concentration distribution of the plasticizer in the rubber compound, as well as the spatiotemporal matching relationship of free radical reactions and chain scission reactions during plasticization. In other words, while existing technology knows that ferrophthalocyanine can be used in combination, it has not further refined the details to how to load, arrange, and construct composite particles to improve the efficiency of medium-temperature plasticization without introducing high environmentally burdensome components.

[0011] Furthermore, from an industrial application perspective, current rubber product manufacturing places higher demands on plasticizer systems. On the one hand, plasticizers need to quickly reach the target Mooney temperature under relatively mild process conditions, thereby reducing plasticizing time, lowering unit energy consumption, and reducing equipment motor load. On the other hand, plasticizer systems are required to avoid using environmentally burdensome halogenated thiophenols and their metal salts as much as possible, and to reduce the potential residues and environmental pressures brought by activators such as zinc, cobalt, and nickel. Existing DBD molding plasticizer routes have a certain foundation in terms of environmental friendliness, but their activity in the mid-temperature range is insufficient. While the phthalocyanine-iron combination route shows potential for improved plasticizing effects, it often lacks targeted design that combines with low-environmentally burdensome components and specific dual-carrier structures. Therefore, under current technological conditions, it is still necessary to further develop a new plasticizer composition and its structural design, which can both inherit the relatively mature industrial applicability of DBD plasticizers and achieve better plasticizing efficiency, energy consumption performance, and equipment operational stability within a mid-temperature plasticizing window of 90–105℃ by introducing more environmentally friendly synergistic plasticizing components and specific phthalocyanine-iron loading structures.

[0012] In summary, while existing technologies disclose two methods: first, a scheme using DBD combined with inert fillers such as kaolin and calcium carbonate to prepare molding plasticizers, such as JP3602610B2; and second, a scheme using ferrophthalocyanine in combination with sulfur-containing compounds such as MBT and DBD for rubber plasticization, such as GB776101A. However, existing technologies have not provided a technical solution that achieves efficient plasticization in the mid-temperature zone, reduces energy consumption, and decreases equipment load without using halogenated thiophenols and their metal salts, or zinc salts or other heavy metal salt-type plasticizing activators. This is achieved by preferentially loading ferrophthalocyanine onto a specific inorganic phase, then compounding it with another inorganic carrier, and finally encapsulating it with a composite particle structure by a main active plasticizer / synergistic plasticizing agent. Therefore, to address these shortcomings, it is still necessary to propose a new environmentally friendly dual-active plasticizer composition and its rubber plasticization method to meet the current comprehensive needs of the rubber processing industry for efficient, energy-saving, low-environmental-impact, and continuous and stable production. Summary of the Invention

[0013] The technical objective of this invention is to address the problems of insufficient plasticization efficiency, high energy consumption, heavy equipment load, and poor environmental friendliness of existing rubber plasticizers under medium-temperature plasticizing conditions, as well as the dependence of some systems on halogenated thiophenols and metal salt activators. This invention provides an environmentally friendly dual-active plasticizer composition for rubber and its rubber plasticizing method. By constructing a composite particle structure with 2,2'-dibenzoylaminodiphenyl disulfide as the main active component, 2-mercaptobenzothiazole as the synergistic component, and combined with phthalocyanine iron-supported dual inorganic carriers, this invention enables natural rubber and other raw rubber to achieve faster viscosity reduction, lower energy consumption, and more stable processing within the medium-temperature plasticizing range of 90–105°C.

[0014] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows:

[0015] An environmentally friendly dual-active plasticizer composition for rubber, comprising, based on 100 parts by total solid mass of the plasticizer composition, the following components:

[0016] 36–44 parts of 2,2'-dibenzoylaminodiphenyl disulfide;

[0017] 1.0–2.6 parts of 2-mercaptobenzothiazole;

[0018] 30-38 parts clay;

[0019] Calcium carbonate 18-24 parts;

[0020] Iron phthalocyanine metal complex, 0.6–1.2 parts;

[0021] in:

[0022] 1) The mass ratio of the 2,2'-dibenzoylaminodiphenyl disulfide to the 2-mercaptobenzothiazole is 18:1 to 32:1;

[0023] 2) The mass ratio of the clay to the calcium carbonate is 1.55:1 to 1.90:1;

[0024] 3) The phthalocyanine iron metal complex is preloaded onto the surface of the clay at 1.5 to 3.0 wt% of the clay mass to form phthalocyanine iron-loaded clay; then the phthalocyanine iron-loaded clay is compounded with the calcium carbonate and mixed with the 2,2'-dibenzoylaminodiphenyl disulfide and the 2-mercaptobenzothiazole to form a composite particle structure with phthalocyanine iron-loaded clay as the core, calcium carbonate as the auxiliary dispersion phase, and the outer layer containing the 2,2'-dibenzoylaminodiphenyl disulfide and the 2-mercaptobenzothiazole.

[0025] Preferably, the 2,2'-dibenzoylaminodiphenyl disulfide has a mass fraction of 38 to 42 parts, the 2-mercaptobenzothiazole has a mass fraction of 1.2 to 2.2 parts, and the mass ratio of the two is 20:1 to 28:1.

[0026] Preferably, the clay is kaolin, and more preferably calcined kaolin; the calcium carbonate is light calcium carbonate, and more preferably light calcium carbonate that has been surface modified with fatty acid or silane coupling agent.

[0027] Preferably, the specific surface area of ​​the phthalocyanine iron metal complex is 10-60 m² / g, and the loading of the phthalocyanine iron metal complex on the clay surface is 1.8-2.6 wt% of the mass of the clay.

[0028] Preferably, the median particle size D50 of the composite particle structure is 20-90 μm, wherein the phthalocyanine iron metal complex is preferentially distributed on the surface of the clay phase inside the particles, and 2,2'-dibenzoylaminodiphenyl disulfide and 2-mercaptobenzothiazole are preferentially distributed on the outer layer of the particles and the pore interface.

[0029] Preferably, in the natural rubber plasticizing test, when the plasticizer composition is added at an amount of 0.25–0.40 phr, the plasticizing temperature is 95–105 °C, and the target Mooney viscosity is [value missing]. Compared to a comparative plasticizer containing only 2,2'-dibenzoylaminodiphenyl disulfide and using the same clay and calcium carbonate ratio but without 2-mercaptobenzothiazole and phthalocyanine iron, the plasticizing time is shortened by no less than 12% and the unit energy consumption is reduced by no less than 8% while achieving the same target Mooney viscosity.

[0030] Furthermore, the present invention also provides a method for preparing the aforementioned environmentally friendly dual-active plasticizer composition for rubber, comprising the following steps:

[0031] S1. Add the phthalocyanine iron metal complex and the clay to a high-speed mixer and dry mix at 30-60℃ for 15-45 minutes to allow the phthalocyanine iron metal complex to be preferentially adsorbed and fixed on the surface of the clay, thus obtaining phthalocyanine iron-loaded clay.

[0032] S2. Mix the phthalocyanine iron-loaded clay with calcium carbonate for 5-20 minutes to obtain a dual inorganic composite carrier.

[0033] S3. Premix 2,2'-dibenzoylaminodiphenyl disulfide with 2-mercaptobenzothiazole at 40-75°C for 5-40 min to obtain a dual-active premix.

[0034] S4. Add the dual-active premix to the dual-inorganic composite carrier and mix at 40-85°C for 5-25 minutes to coat the surface of the dual-inorganic composite carrier with the dual-active premix.

[0035] S5. Granulate or crush and shape the material obtained in step S4 to obtain the environmentally friendly dual-active plasticizer composition for rubber.

[0036] Preferably, the high-speed mixer in step S1 operates at a speed of 600–1800 rpm;

[0037] And / or, the median particle size D50 of the material obtained after mixing in step S4 is controlled to be 20–90 μm.

[0038] And / or, 2,2'-dibenzoylaminodiphenyl disulfide and 2-mercaptobenzothiazole are not added between steps S1 and S2 to ensure that phthalocyanine iron is preferentially loaded on the clay surface.

[0039] Furthermore, the present invention also provides a rubber plasticizing method using the aforementioned environmentally friendly dual-active plasticizer composition, comprising the following steps:

[0040] S1. Add the raw rubber to be plasticized into an open mill or internal mixer, and pre-plasticize it for 0.5 to 3 minutes at a roller temperature or barrel temperature of 90 to 105°C.

[0041] S2. Within 0 to 3 minutes before or after the end of pre-plasticizing, add 0.25 to 0.40 phr of the environmentally friendly dual-active plasticizer composition for rubber to the raw rubber.

[0042] S3. Continue plasticizing for 8-20 minutes until the Mooney viscosity of the rubber drops to the preset target range;

[0043] S4. Record the Mooney viscosity, plasticizing time, unit energy consumption and motor load at the end of plasticizing, and terminate plasticizing when the target Mooney viscosity is met.

[0044] Preferably, the raw rubber is natural rubber, or a blend of natural rubber and at least one of butadiene rubber, styrene-butadiene rubber, and isoprene rubber.

[0045] Preferably, the environmentally friendly dual-active plasticizer composition for rubber is dispersed within 2 to 6 minutes after being added to the rubber;

[0046] Further optimization yielded a target Mooney viscosity of Furthermore, in plasticizing batches using the aforementioned environmentally friendly dual-active plasticizer composition for rubber, the peak motor load is no higher than 85% of the peak motor load of the comparative process without plasticizer.

[0047] In a further preferred embodiment, the environmentally friendly dual-active plasticizer composition for rubber is first mixed with a portion of raw rubber to obtain a plasticizer masterbatch, and then the remaining raw rubber is added at the initial stage of plasticizing.

[0048] This invention utilizes 2,2'-dibenzoylaminodiphenyl disulfide as the main active plasticizer and 2-mercaptobenzothiazole as a synergistic plasticizer. Combined with a structural design where phthalocyanine iron is preferentially loaded onto the surface of clay, then compounded with calcium carbonate, and finally coated by the dual active components to form composite particles, this plasticizer not only possesses good storage stability, flowability, and feeding uniformity, but also achieves faster dispersion and more effective synergistic effects during rubber plasticizing. Compared to existing conventional carrier-type plasticizers based on DBD, this invention can achieve faster dispersion within the medium-temperature plasticizing range of 90–105°C. This invention reduces the Mooney viscosity of raw rubber such as natural rubber, significantly shortens the plasticizing time required to achieve the target plasticity, reduces unit energy consumption and peak motor load of equipment, improves temperature rise control and operational stability during the plasticizing process, thereby expanding the process operation window and reducing batch-to-batch fluctuations. At the same time, this invention does not use pentachlorothiophenol, pentachlorothiophenol and its metal salts, zinc salts of fatty acids and other heavy metal salts as plasticizing activators. While maintaining high plasticizing efficiency, it reduces the environmental burden caused by halogenated thiophenols and heavy metal sources, making the resulting plasticizer system more in line with the development requirements of green manufacturing and cleaner rubber processing. Attached Figure Description

[0049] Figure 1 This is a schematic diagram of the preparation process of the plasticizer composition of the present invention.

[0050] Figure 2 This is a schematic diagram of the rubber plasticizing process using the plasticizer composition of the present invention.

[0051] Figure 3 A comparison chart showing the plasticizing time required for different plasticizer systems to reach the target Mooney viscosity.

[0052] Figure 4 A comparison chart of unit energy consumption for different plasticizer systems.

[0053] Figure 5 A comparison chart of peak motor loads for different plasticizer systems.

[0054] Figure 6 The graph shows the Mooney viscosity of different plasticizer systems as a function of time during the plasticizing process.

[0055] Figure 7 This is a graph showing the change of motor load over time during the plasticizing process for different plasticizer systems.

[0056] Figure 8 A comparison chart showing the plasticizing time required to reach the target Mooney temperature under different plasticizing conditions. Detailed Implementation

[0057] The technical solution of the present invention will be further described in detail below with reference to the embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and are not intended to limit the scope of protection of the present invention. Equivalent substitutions or conventional adjustments made by those skilled in the art to the raw material type, equipment specifications, and specific operating parameters without departing from the spirit and substance of the present invention should all fall within the scope of protection of the present invention.

[0058] This invention provides an environmentally friendly dual-active plasticizer composition for rubber and a rubber plasticizing method thereof. The composition uses 2,2'-dibenzoylaminodiphenyl disulfide as the main active plasticizer component and 2-mercaptobenzothiazole as a synergistic plasticizer component. It achieves rapid viscosity reduction, lower energy consumption, and lower equipment load peaks within the medium-temperature plasticizing range of 90–105°C, while avoiding the use of pentachlorothiophenol, pentachlorothiophenol and its metal salts, zinc fatty acid salts, and other heavy metal salt-type plasticizer activators.

[0059] I. Raw Materials, Equipment and Testing Methods

[0060] 1. Raw materials

[0061] The raw materials used in this embodiment are as follows:

[0062] 2,2'-Dibenzoylaminodiphenyl disulfide (DBD): Industrial grade, purity not less than 98%, light yellow powder;

[0063] 2-Mercaptobenzothiazole (MBT): Industrial grade, purity not less than 97%, light yellow powder;

[0064] Ferrophthalocyanine (FePc): Industrial grade powder with a specific surface area of ​​approximately 25–40 m² / g;

[0065] Clay: preferably calcined kaolin with a median particle size D50 of about 4 to 8 μm;

[0066] Calcium carbonate: preferably light calcium carbonate with a median particle size D50 of about 2 to 5 μm; some embodiments use light calcium carbonate with a surface modified by fatty acids.

[0067] Natural rubber: Standard natural rubber SVR10 is used;

[0068] Other excipients: Pentachlorothiophenol, pentachlorothiophenol and their metal salts were not used, nor were zinc salts of fatty acids or other heavy metal salt-type plasticizers.

[0069] 2. Main Equipment

[0070] The SHR type high-speed mixer has an adjustable speed range of 300 to 2000 rpm;

[0071] Constant temperature stirred tank with jacket heating function;

[0072] Small cooling granulator;

[0073] Laboratory airflow shaping machine or mechanical crushing shaping machine;

[0074] 1.6L experimental internal mixer with adjustable rotor speed;

[0075] XK-160 open mill;

[0076] Mooney viscometer;

[0077] Electrical parameter recording module, used for collecting unit energy consumption and motor load peak;

[0078] Laser particle size analyzer;

[0079] Scanning electron microscope (used to assist in observing particle distribution morphology, this item is only for illustrating particle structure characteristics and is not necessary for implementing the present invention).

[0080] 3. Test Methods

[0081] 3.1 Mooney Viscosity Test

[0082] The Mooney viscosity of the rubber compound is determined according to the conventional method in the rubber industry, and the test conditions are as follows:

[0083] $$M_L(1+4)100^\circC$$

[0084] wherein, the preheating time is 1 min, the rotor running time is 4 min, and the test temperature is 100°C. The test result is the average value of 3 parallel samples.

[0085] 3.2 Unit Energy Consumption

[0086] The unit energy consumption is measured by the electrical parameter recording module supporting the internal mixer, and the total power consumption is converted into power consumption per ton of rubber, with the unit of kWh / t. The calculation formula is as follows:

[0087] $$E=\frac{W}{m}$$

[0088] wherein, $E$ is the unit energy consumption, in kWh / t; $W$ is the total power consumption in the plastication stage, in kWh; $m$ is the converted mass of the rubber compound of this batch, in t.

[0089] 3.3 Motor Load Peak

[0090] The motor load peak is expressed as the highest instantaneous load percentage collected during the whole plastication process, and the relative rated load percentage is recorded with reference to the blank process without peptizer.

[0091] 3.4 Dispersion Time Determination

[0092] After adding the plasticizer to the internal mixer, the time required for the plasticizer to complete basic dispersion is determined by the standard that the torque curve tends to be stable and there are no obvious undispersed particles in the sample film.

[0093] 3.5 Plasticizing time

[0094] Plasticizing time refers to the time from the addition of the plasticizer until the Mooney viscosity reaches the target value. Total time required.

[0095] II. General preparation method of the plasticizer composition of the present invention

[0096] The plasticizer composition of the present invention is prepared by a process route of first loading, then compounding, and then coating. The general preparation steps are as follows.

[0097] Step A: Phthalocyanine iron is preferentially loaded onto the clay surface

[0098] Weigh out the clay and phthalocyanine iron according to the formula, add them to a high-speed mixer, and dry mix at 30–60°C, preferably 40–55°C, for 15–45 minutes, with the speed controlled at 600–1800 rpm. This step allows phthalocyanine iron to be preferentially adsorbed and fixed on the surface of the clay, resulting in phthalocyanine iron-loaded clay.

[0099] Step B: Combine with calcium carbonate to form a dual inorganic composite carrier.

[0100] Weighed calcium carbonate is added to the phthalocyanine iron-supported clay obtained in step A, and mixing continues for 5–20 minutes to ensure that the calcium carbonate is evenly distributed in the carrier system, forming a dual-inorganic composite carrier. In this step, calcium carbonate is mainly used to adjust the brittleness, flowability, and subsequent dispersion path in the rubber.

[0101] Step C: Premixing of dual active components

[0102] Weigh DBD and MBT according to the formula, and premix them in a constant temperature stirred tank at 40–75°C for 5–40 min, preferably at 50–65°C. This step ensures that MBT is more uniformly distributed in DBD, resulting in a dual-active premix.

[0103] Step D: Coating final mix

[0104] The dual-active premix obtained in step C is added to the dual-inorganic composite carrier obtained in step B, and mixed at 40-85°C for 5-25 minutes to coat the dual-active components on the surface and pore interface of the dual-inorganic composite carrier, forming a composite particle precursor.

[0105] Step E: Granulation or shaping

[0106] The material obtained in step D is cooled and granulated or pulverized and shaped to control the median particle size D50 to be 20–90 μm, thus obtaining the plasticizer composition of the present invention. The resulting product has good flowability, is not prone to significant agglomeration, and is easy to meter and add.

[0107] III. General Steps of the Rubber Plasticizing Method of the Present Invention

[0108] 1) 100 parts by weight of natural rubber SVR10 were fed into an experimental internal mixer;

[0109] 2) Set the internal mixer barrel temperature or equivalent plasticizing temperature to 90–105℃;

[0110] 3) Pre-plasticize for 0.5–3 minutes to initially soften the raw rubber;

[0111] 4) Add the plasticizer composition of the present invention according to the dosage specified in the examples;

[0112] 5) Continue plasticizing, and record changes in torque, energy consumption, and motor load in real time;

[0113] 6) Periodically sample and test Mooney viscosity; when Mooney viscosity reaches... Plasticizing was terminated when the temperature reached 50±2°C.

[0114] 7) Record the plasticizing time, unit energy consumption, peak motor load, and plasticizer dispersion time.

[0115] Unless otherwise stated, in all the following examples and comparative examples, the amount of plasticizer used is 0.30 phr, that is, 0.30 parts by weight of plasticizer is added for every 100 parts by weight of rubber.

[0116] IV. Examples

[0117] The following examples illustrate that, within the scope defined by the claims of this invention, by adjusting the specific proportions of DBD, MBT, clay, calcium carbonate, and ferrocyanine, as well as the preparation conditions, the same technical effects can be achieved. That is, within the medium-temperature plasticizing window of 90–105°C, compared with ordinary DBD carrier-type plasticizers and several control schemes, it exhibits faster viscosity reduction, lower energy consumption, and lower peak motor load.

[0118] Example 1

[0119] 1. Formulation composition (based on 100 parts by total mass of plasticizer solids)

[0120] DBD: 40.0 copies

[0121] MBT: 1.8 copies

[0122] Clay: 34.5 parts

[0123] Calcium carbonate: 22.5 parts

[0124] Ferrophthalocyanine: 1.2 parts

[0125] The DBD / MBT mass ratio was 22.22:1, the clay / calcium carbonate mass ratio was 1.53:1, and the phthalocyanine iron loading was approximately 3.48 wt% of the clay mass.

[0126] 2. Preparation steps

[0127] (1) Add 34.5 parts of clay and 1.2 parts of phthalocyanine iron to a high-speed mixer and dry mix for 30 min at 50℃ and 1200 rpm to obtain phthalocyanine iron-loaded clay;

[0128] (2) Add 22.5 parts of calcium carbonate and mix for 10 min to obtain a dual inorganic composite carrier;

[0129] (3) Premix 40.0 parts of DBD and 1.8 parts of MBT in a constant temperature stirred tank at 60℃ for 20 min to obtain a dual-active premix;

[0130] (4) Add the dual-active premix to the dual-inorganic composite carrier and mix at 65°C for 15 min;

[0131] (5) After cooling, granulation and shaping, the resulting particles have a D50 of approximately 58 μm.

[0132] 3. Plasticizing process

[0133] 100 parts of SVR10 natural rubber were put into a 1.6L internal mixer, the barrel temperature was set to 100℃ and the rotor speed was 60rpm. After pre-plasticizing for 1.5min, 0.30phr of the plasticizer composition of this example was added, and plasticizing was continued and samples were taken for Mooney testing.

[0134] 4. Test Results

[0135] The plasticizing time for Mooney to reach the target value was 31 minutes, the unit energy consumption was 86 kWh / t, the peak motor load was 78%, and the distributed completion time was 3.5 minutes.

[0136] Example 2

[0137] 1. Formula Composition

[0138] DBD: 38.5 copies

[0139] MBT: 1.6 copies

[0140] Clay: 36.0 parts

[0141] Calcium carbonate: 22.7 parts

[0142] Ferrophthalocyanine: 1.2 parts

[0143] The mass ratio of DBD / MBT is 24.06:1, and the mass ratio of clay / calcium carbonate is 1.59:1.

[0144] 2. Preparation steps

[0145] (1) Clay and ferrophthalocyanine were mixed at 45°C and 1000 rpm for 25 min;

[0146] (2) After adding calcium carbonate, continue mixing for 12 minutes;

[0147] (3) DBD and MBT were premixed at 55℃ for 15 min;

[0148] (4) Mix at 60℃ for 18 min;

[0149] (5) The D50 after crushing and shaping is 46μm.

[0150] 3. Plasticizing process

[0151] Same as in Example 1, but the plasticizing temperature was set to 98°C.

[0152] 4. Test Results

[0153] Plasticizing time: 32 min; unit energy consumption: 87 kWh / t; peak motor load: 79%; dispersion time: 3.2 min.

[0154] Example 3

[0155] 1. Formula Composition

[0156] DBD: 41.0 copies

[0157] MBT: 1.5 copies

[0158] Clay: 34.0 parts

[0159] Calcium carbonate: 22.5 parts

[0160] Ferrophthalocyanine: 1.0 part

[0161] The mass ratio of DBD / MBT is 27.33:1, and the mass ratio of clay / calcium carbonate is 1.51:1.

[0162] 2. Preparation steps

[0163] (1) Clay and ferrophthalocyanine were mixed at 52°C and 1300 rpm for 35 min;

[0164] (2) After adding calcium carbonate, continue mixing for 8 minutes;

[0165] (3) DBD and MBT were premixed at 62℃ for 18 min;

[0166] (4) Mix at 68℃ for 12 min;

[0167] (5) The D50 after granulation is 63 μm.

[0168] 3. Plasticizing process

[0169] Same as in Example 1, the temperature was 102°C.

[0170] 4. Test Results

[0171] Plasticizing time: 30 min; unit energy consumption: 84 kWh / t; peak motor load: 76%; dispersion time: 3.8 min.

[0172] Example 4

[0173] 1. Formula Composition

[0174] DBD: 39.0 copies

[0175] MBT: 2.0 copies

[0176] Clay: 33.5 parts

[0177] Calcium carbonate: 24.0 parts

[0178] Ferrophthalocyanine: 1.5 parts

[0179] The DBD / MBT mass ratio is 19.5:1, and the clay / calcium carbonate mass ratio is 1.40:1. This formulation is close to the edge values ​​of the claims and was used to verify its feasibility at higher MBT and higher FePc levels.

[0180] 2. Preparation steps

[0181] (1) Clay and ferrophthalocyanine were mixed at high speed at 48℃ for 28 min;

[0182] (2) Mix after adding calcium carbonate for 10 minutes;

[0183] (3) DBD and MBT were premixed at 58℃ for 20 min;

[0184] (4) Mix at 65℃ for 15 min and mechanically shape to obtain particles with D50 of 54 μm.

[0185] 3. Plasticizing process

[0186] The temperature was 100°C, and everything else was the same as in Example 1.

[0187] 4. Test Results

[0188] Plasticizing time: 31 min; unit energy consumption: 86 kWh / t; peak motor load: 78%; dispersion time: 3.4 min.

[0189] Example 5

[0190] 1. Formula Composition

[0191] DBD: 42.0 copies

[0192] MBT: 1.3 copies

[0193] Clay: 34.2 parts

[0194] Calcium carbonate: 21.5 parts

[0195] Ferrophthalocyanine: 1.0 part

[0196] The mass ratio of DBD / MBT is 32.31:1, and the mass ratio of clay / calcium carbonate is 1.59:1.

[0197] 2. Preparation steps

[0198] (1) FePc was first loaded with clay under the conditions of 55℃, 1400rpm, and 30min;

[0199] (2) Add calcium carbonate and mix for 9 minutes;

[0200] (3) DBD and MBT were premixed at 60℃ for 25 min;

[0201] (4) Final mix at 70℃ for 10 min;

[0202] (5) The D50 after shaping is 51 μm.

[0203] 3. Plasticizing process

[0204] Plasticizing temperature: 95℃.

[0205] 4. Test Results

[0206] Plasticizing time: 33 min; unit energy consumption: 89 kWh / t; peak motor load: 80%; dispersion time: 3.6 min.

[0207] Example 6

[0208] 1. Formula Composition

[0209] DBD: 38.0 copies

[0210] MBT: 2.1 copies

[0211] Clay: 35.0 parts

[0212] Calcium carbonate: 23.7 parts

[0213] Ferrophthalocyanine: 1.2 parts

[0214] The mass ratio of DBD / MBT is 18.10:1, and the mass ratio of clay / calcium carbonate is 1.48:1.

[0215] 2. Preparation steps

[0216] (1) Iron phthalocyanine was mixed with clay at 50°C and 1100 rpm for 30 min;

[0217] (2) Add calcium carbonate and mix for 15 minutes;

[0218] (3) DBD and MBT were premixed at 57℃ for 15 min;

[0219] (4) Final mixing temperature 62℃, time 20min;

[0220] (5) D50 is approximately 49 μm.

[0221] 3. Plasticizing process

[0222] Plasticizing temperature 100℃.

[0223] 4. Test Results

[0224] Plasticizing time: 31 min; unit energy consumption: 86 kWh / t; peak motor load: 78%; dispersion time: 3.1 min.

[0225] V. Comparative Examples

[0226] The following comparative examples are used to demonstrate that when the key technical features of the present invention are deviated from, for example, only DBD agent is used, MBT is removed, FePc is removed, ordinary blending is used instead of pre-loaded structure, or the key proportions are deviated from the scope of the claims of the present invention, the plasticizing efficiency, energy consumption and motor load will all deteriorate to varying degrees, thus proving that the technical effect of the present invention cannot be obtained by simply adding any components.

[0227] Comparative Example 1: Common carrier-type plasticizers containing only DBD

[0228] 1. Formula Composition

[0229] DBD: 40.0 copies

[0230] MBT: 0 copies

[0231] Clay: 36.0 parts

[0232] Calcium carbonate: 24.0 parts

[0233] Ferrophthalocyanine: 0 parts

[0234] 2. Preparation method

[0235] All components are directly mixed and then granulated, without using the FePc supported structure or containing MBT.

[0236] 3. Plasticizing results

[0237] At 100℃ and 0.30phr, the plasticizing time required to reach the target Mooney is 40min, the unit energy consumption is 100kWh / t, the peak motor load is 86%, and the dispersion time is 4.8min.

[0238] Comparative Example 2: DBD + FePc, but without MBT

[0239] 1. Formula Composition

[0240] DBD: 40.0 copies

[0241] MBT: 0 copies

[0242] Clay: 34.8 parts

[0243] Calcium carbonate: 24.0 parts

[0244] Ferrophthalocyanine: 1.2 parts

[0245] 2. Preparation method

[0246] The same FePc preloaded clay method as in Example 1 was used, but MBT was not added.

[0247] 3. Plasticizing results

[0248] Plasticizing time: 36 min; unit energy consumption: 94 kWh / t; peak motor load: 82%; dispersion time: 4.0 min.

[0249] Comparative Example 3: MBT + FePc, but without DBD

[0250] 1. Formula Composition

[0251] DBD: 0 copies

[0252] MBT: 2.0 copies

[0253] Clay: 52.0 parts

[0254] Calcium carbonate: 44.8 parts

[0255] Ferrophthalocyanine: 1.2 parts

[0256] 2. Preparation method

[0257] The method involves first loading FePc onto the surface of clay, then adding calcium carbonate, and finally dispersing and coating MBT.

[0258] 3. Plasticizing results

[0259] Plasticizing time: 38 min; unit energy consumption: 97 kWh / t; peak motor load: 84%; dispersion time: 4.5 min.

[0260] Comparative Example 4: The components are the same as those of the present invention, but ordinary blending is used instead of the previous loading, compounding, and coating process.

[0261] 1. Formula Composition

[0262] Same as in Example 1:

[0263] DBD: 40.0 copies

[0264] MBT: 1.8 copies

[0265] Clay: 34.5 parts

[0266] Calcium carbonate: 22.5 parts

[0267] Ferrophthalocyanine: 1.2 parts

[0268] 2. Preparation method

[0269] All components were added to the mixer at once and mixed directly for 20 minutes before granulation. FePc preferential loading of clay was not performed, nor was a process design of premixing with dual activity followed by coating performed.

[0270] 3. Plasticizing results

[0271] Plasticizing time: 35 min; unit energy consumption: 92 kWh / t; peak motor load: 81%; dispersion time: 4.2 min.

[0272] Comparative Example 5: The DBD / MBT ratio deviates from the preferred range of the present invention.

[0273] 1. Formula Composition

[0274] DBD: 30.0 copies

[0275] MBT: 5.0 copies

[0276] Clay: 39.0 parts

[0277] Calcium carbonate: 24.8 parts

[0278] Ferrophthalocyanine: 1.2 parts

[0279] The DBD / MBT mass ratio is only 6:1, which is significantly lower than the preferred range of this invention.

[0280] 2. Preparation method

[0281] The same loading, compounding, and coating method as in Example 1 was adopted.

[0282] 3. Plasticizing results

[0283] The plasticizing time was 37 minutes, the unit energy consumption was 95 kWh / t, the peak motor load was 83%, the dispersion time was 3.9 minutes, and the film showed slight odor enhancement and surface unevenness.

[0284] Comparative Example 6: The clay / calcium carbonate ratio deviates from the preferred range of this invention.

[0285] 1. Formula Composition

[0286] DBD: 40.0 copies

[0287] MBT: 1.8 copies

[0288] Clay: 24.0 parts

[0289] Calcium carbonate: 33.0 parts

[0290] Ferrophthalocyanine: 1.2 parts

[0291] The clay / calcium carbonate mass ratio is 0.73:1, which is significantly low.

[0292] 2. Preparation method

[0293] The same preparation method as in Example 1 was used.

[0294] 3. Plasticizing results

[0295] Plasticizing time: 36 min; unit energy consumption: 93 kWh / t; peak motor load: 82%; dispersion time: 4.1 min.

[0296] VI. Summary of Results from Examples and Comparative Examples

[0297] Table 1 Summary of formulations and performance of each embodiment and comparative example

[0298]

[0299] VII. Technical Effect Analysis

[0300] 1. All embodiments of the present invention can achieve essentially the same effect within the scope of the claims.

[0301] As can be seen from Examples 1 to 6, within the scope defined by the claims of this invention, even with certain variations in the proportions of DBD, MBT, kaolin, calcium carbonate, and ferrocyanine, and with the plasticizing temperature fluctuating between 95 and 102°C, each example can stably reduce the Mooney viscosity of natural rubber to a value within 30 to 33 minutes. Within the target range of 50±2, the unit energy consumption is maintained between 84 and 89 kWh / t, the peak motor load is maintained between 76% and 80%, and the plasticizer dispersion time is maintained between 3.1 and 3.8 min.

[0302] 2. Compared with ordinary carrier-type plasticizers containing only DBD, the present invention has significant energy-saving and efficiency-improving effects.

[0303] Comparing Example 1 with Comparative Example 1, it can be seen that under the same plasticizing temperature of 100°C, the same feed rate of 0.30 phr, and the same target Mooney conditions:

[0304] The plasticizing time was reduced from 40 minutes to 31 minutes, a reduction of 22.5%.

[0305] Energy consumption per unit decreased from 100 kWh / t to 86 kWh / t, a reduction of 14.0%;

[0306] The peak motor load decreased from 86% to 78%, a drop of 8 percentage points;

[0307] The dispersion time was reduced from 4.8 minutes to 3.5 minutes.

[0308] This indicates that, by introducing the MBT synergistic component and the FePc-supported dual-carrier structure, the plasticizing efficiency in the mid-temperature range is significantly improved compared to traditional DBD carrier plasticizers.

[0309] 3. Simply adding FePc or simply using MBT+FePc cannot achieve the comprehensive effect of this invention.

[0310] Comparative Example 2 illustrates the case of DBD+FePc but without MBT. Although its plasticizing time and energy consumption are better than Comparative Example 1, it is still significantly inferior to Example 1. This demonstrates that simply introducing FePc is insufficient to achieve the effects of this invention, and MBT plays a non-negligible role as a synergistic plasticizing component.

[0311] Comparative Example 3 was used to illustrate the case of MBT+FePc but without DBD. The results showed that this scheme still could not achieve rapid viscosity reduction, indicating that DBD is irreplaceable as the main active plasticizing component.

[0312] 4. The technical effects of this invention come not only from the selection of components, but also from the specific particle structure.

[0313] Comparative Example 4 has the same chemical composition as Example 1, the only difference being the preparation process and the internal structure of the particles: Example 1 uses a composite particle process in which FePc is preferentially loaded with clay, then compounded with calcium carbonate, and finally coated with DBD / MBT, while Comparative Example 4 uses a one-time ordinary blending of all components.

[0314] The results showed that the plasticizing time of Comparative Example 4 was 35 min, which was 4 min longer than that of Example 1; the unit energy consumption was 92 kWh / t, which was 6 kWh / t higher than that of Example 1; the peak motor load was 81%, which was higher than that of Example 1 (78%); and the dispersion time was also significantly longer.

[0315] This result directly demonstrates that the technical effect of this invention cannot be simply attributed to the selection of these components, but is closely related to their spatial distribution structure within the particles. FePc preferentially supports the clay surface, which is beneficial for the formation of catalytic active centers in the particle core; calcium carbonate, as an auxiliary dispersed phase, facilitates particle breakage and diffusion under intense mixing shear; DBD and MBT are located in the outer layer and interfacial region, which is beneficial for rapid release and initiation of the plasticization reaction in the rubber compound. It is precisely this specific structure that enables this invention to achieve superior plasticizing effects in the mid-temperature range.

[0316] 5. When the key ratio deviates, the technical effect decreases.

[0317] Comparative Example 5 shows that when the DBD / MBT ratio is too low and MBT is relatively excessive, even with the retention of the structural process of this invention, the plasticizing time and energy consumption still deteriorate significantly, and the process stability decreases. This indicates that the DBD / MBT ratio cannot be arbitrarily selected; it must be controlled within the range defined by this invention to balance the primary plasticizing activity and the synergistic plasticizing effect.

[0318] Comparative Example 6 shows that when the clay / calcium carbonate ratio deviates from the preferred range of this invention, the functional division of the particles as carriers is disrupted, the structural advantage of FePc preferentially loading clay cannot be fully realized, ultimately leading to a decrease in plasticizing efficiency. This demonstrates that setting the ratio of the two inorganic carriers also has clear technical significance.

[0319] In this embodiment, although natural rubber SVR10 is preferred as the raw rubber for verification, those skilled in the art should understand that the plasticizer composition of this invention is also applicable to blended systems composed of natural rubber and at least one of butadiene rubber, styrene-butadiene rubber, and isoprene rubber. In actual industrial production, the amount of plasticizer can be routinely fine-tuned according to the equipment type, loading amount, rotation speed, and target Mooney requirements. For example, the feed amount can be optimized within the range of 0.25 to 0.40 phr; or a suitable medium-temperature plasticizing window can be selected within the range of 95 to 105°C. Such adjustments are conventional technical means that can be directly implemented by those skilled in the art based on the content of this specification and do not affect the essence of this invention.

[0320] Furthermore, calcined kaolin is preferably used as the clay and lightweight calcium carbonate as the auxiliary carrier in this invention. However, as long as phthalocyanine iron can be preferentially loaded onto the surface of the clay phase and the dual active components can be coated on the surface and pore interface of the composite carrier in the final mixing stage, equivalent types of clay or calcium carbonate of equivalent specifications can also be used. The granulation method, shaping method, and particle size control method can also be adapted to the equipment conditions.

[0321] In summary, this invention, by constructing a composite particle structure consisting of a DBD main active component, an MBT synergistic component, FePc preferentially loaded clay, a clay / calcium carbonate dual inorganic composite carrier, and an outer coating of dual active components, achieves rapid viscosity reduction, lower energy consumption, lower equipment load peaks, and better process stability within the medium-temperature plasticizing range of 90–105°C, without using halogenated thiophenols and their metal salts, zinc fatty acid salts, or other heavy metal salt-type plasticizers. Multiple embodiments demonstrate that essentially the same technical effects can be achieved within the scope defined by the claims of this invention; multiple comparative examples further demonstrate that the technical effects of this invention stem from the synergy of specific component selection, specific proportion ranges, and specific composite particle structure, and cannot be obtained through simple mixing of conventional components in existing technologies.

[0322] The foregoing description of embodiments of the present invention, through which those skilled in the art are able to implement or use the present invention, will be readily apparent to those skilled in the art. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novelty disclosed herein.

Claims

1. An environmentally friendly dual-active plasticizer composition for rubber, characterized in that, The plasticizer composition, based on a total solid mass of 100 parts, comprises the following components: 36-44 parts of 2,2'-dibenzoylaminodiphenyl disulfide; 1.0-2.6 parts of 2-mercaptobenzothiazole; 30-38 parts of kaolin; 18-24 parts of calcium carbonate; and 0.6-1.2 parts of phthalocyanine iron metal complex. Wherein: 1) the mass ratio of the 2,2'-dibenzoylaminodiphenyl disulfide to the 2-mercaptobenzothiazole is 18:1 to 32:1; 2) the mass ratio of the clay to the calcium carbonate is 1.55:1 to 1.90:1; 3) the phthalocyanine iron metal complex is preloaded onto the surface of the clay at 1.5 to 3.0 wt% of the clay mass to form phthalocyanine iron-loaded clay; subsequently, the phthalocyanine iron-loaded clay is compounded with the calcium carbonate and mixed with the 2,2'-dibenzoylaminodiphenyl disulfide and the 2-mercaptobenzothiazole to form a composite particle structure with phthalocyanine iron-loaded clay as the core, calcium carbonate as the auxiliary dispersed phase, and the outer layer containing the 2,2'-dibenzoylaminodiphenyl disulfide and the 2-mercaptobenzothiazole.

2. The environmentally friendly dual-active plasticizer composition for rubber as described in claim 1, characterized in that, The 2,2'-dibenzoylaminodiphenyl disulfide has a mass fraction of 38 to 42 parts, the 2-mercaptobenzothiazole has a mass fraction of 1.2 to 2.2 parts, and the mass ratio of the two is 20:1 to 28:

1.

3. The environmentally friendly dual-active plasticizer composition for rubber as described in claim 1, characterized in that, The clay is kaolin, preferably calcined kaolin; the calcium carbonate is light calcium carbonate, preferably light calcium carbonate that has been surface modified with fatty acid or silane coupling agent.

4. The environmentally friendly dual-active plasticizer composition for rubber as described in claim 1, characterized in that, The specific surface area of ​​the phthalocyanine iron metal complex is 10–60 m². 2 / g, the loading amount of the phthalocyanine iron metal complex on the surface of the clay is 1.8 to 2.6 wt% of the mass of the clay.

5. The environmentally friendly dual-active plasticizer composition for rubber as described in claim 1, characterized in that, The median particle size D50 of the composite particle structure is 20-90 μm, and the phthalocyanine iron metal complex is preferentially distributed on the surface of the clay phase inside the particles, while 2,2'-dibenzoylaminodiphenyl disulfide and 2-mercaptobenzothiazole are preferentially distributed on the outer layer of the particles and the pore interface.

6. The environmentally friendly dual-active plasticizer composition for rubber as described in claim 1, characterized in that, In the plasticizing test of natural rubber, when the plasticizer composition was added at a dosage of 0.25–0.40 phr, the plasticizing temperature was 95–105 °C, and the target Mooney viscosity was [value missing]. Compared to a comparative plasticizer containing only 2,2'-dibenzoylaminodiphenyl disulfide and using the same clay and calcium carbonate ratio but without 2-mercaptobenzothiazole and phthalocyanine iron, the plasticizing time is shortened by no less than 12% and the unit energy consumption is reduced by no less than 8% while achieving the same target Mooney viscosity.

7. A method for preparing an environmentally friendly dual-active plasticizer composition for rubber according to any one of claims 1 to 6, characterized in that, The process includes the following steps: S1, adding phthalocyanine iron metal complex and clay to a high-speed mixer and dry mixing at 30-60°C for 15-45 min, so that the phthalocyanine iron metal complex is preferentially adsorbed and fixed on the surface of the clay, to obtain phthalocyanine iron-loaded clay; S2, mixing the phthalocyanine iron-loaded clay with calcium carbonate for 5-20 min, to obtain a dual-inorganic composite carrier; S3, premixing 2,2'-dibenzoylaminodiphenyl disulfide and 2-mercaptobenzothiazole at 40-75°C for 5-40 min, to obtain a dual-active premix; S4, adding the dual-active premix to the dual-inorganic composite carrier and mixing at 40-85°C for 5-25 min, so that the dual-active premix coats the surface of the dual-inorganic composite carrier; S5, granulating or pulverizing the material obtained in step S4 to obtain the environmentally friendly dual-active plasticizer composition for rubber.

8. The preparation method according to claim 7, characterized in that, The high-speed mixer mentioned in step S1 has a rotational speed of 600 to 1800 rpm; And / or, the median particle size D50 of the material obtained after mixing in step S4 is controlled to be 20-90 μm; And / or, 2,2'-dibenzoylaminodiphenyl disulfide and 2-mercaptobenzothiazole are not added between steps S1 and S2 to ensure that phthalocyanine iron is preferentially loaded on the clay surface.

9. A rubber plasticizing method using the environmentally friendly dual-active plasticizer composition for rubber according to any one of claims 1 to 6, characterized in that, The process includes the following steps: S1, adding the raw rubber to be plasticized into an open mill or internal mixer, and pre-plasticizing at a roller temperature or barrel temperature of 90-105°C for 0.5-3 minutes; S2, adding 0.25-0.40 phr of the environmentally friendly dual-active plasticizer composition for rubber to the raw rubber within 0-3 minutes before or after the end of pre-plasticizing; S3, continuing plasticizing for 8-20 minutes to reduce the Mooney viscosity of the rubber to a preset target range; S4, recording the Mooney viscosity, plasticizing time, unit energy consumption, and motor load at the end of plasticizing, and terminating plasticizing when the target Mooney viscosity is met.

10. The rubber plasticizing method as described in claim 9, characterized in that, The raw rubber is natural rubber, or a blend of natural rubber with at least one of butadiene rubber, styrene-butadiene rubber, and isoprene rubber. Preferably, the environmentally friendly dual-active plasticizer composition for rubber is dispersed within 2 to 6 minutes after being added to the rubber; Preferably, the target Mooney viscosity is Furthermore, in plasticizing batches using the aforementioned environmentally friendly dual-active plasticizer composition for rubber, the peak motor load is no higher than 85% of the peak motor load of the comparative process without plasticizer. Preferably, the environmentally friendly dual-active plasticizer composition for rubber is first mixed with a portion of raw rubber to obtain a plasticizer masterbatch, and then the remaining raw rubber is added at the initial stage of plasticizing.

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