High bio-based elastomer cord rubber composition

Abstract

The present invention provides a high bio-based elastomer cord rubber composition, which relates to the technical field of rubber compositions. The rubber composition is mainly obtained by compounding natural rubber, porous three-phase alloy, rice husk white carbon black, silane coupling agent, zinc oxide, anti-aging agent, cobalt salt, methylene donor, methylene acceptor, insoluble sulfur, accelerator, and deep eutectic solvent in a specific proportion. The cord rubber prepared from the high bio-based elastomer cord rubber composition of the present application has excellent thermal conductivity, low heat generation, and high fatigue performance, and can fully meet the requirements of high adhesion and low heat generation performance of tire cord rubber.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber compositions, and particularly to a high bio-based elastomer cord rubber composition. Background Art

[0002] Among the raw materials used in tire production, most of the raw materials rely heavily on rubber materials synthesized from fossil resources, with high carbon emissions, which is very unfavorable for the sustainable development of the tire industry.

[0003] In recent years, as a renewable raw material, bio-based filler rice husk silica white has been widely used in the preparation of each rubber layer of bio-based tires to equivalently replace highly dispersible silica white. It not only reduces the production cost of tires, but also realizes the high-value utilization of biomass resources, greatly alleviating the consumption pressure and dependence on petrochemical resources. It is an important direction for the low-carbon and green development of the future tire industry.

[0004] The existing belt layer rubber (prepared from cord rubber) of tires requires excellent thermal conductivity, low heat generation, heat resistance adhesion, and high fatigue performance. After using the bio-based filler rice husk silica white, the adhesion performance of the rubber compound is significantly improved, and the formed resorcinol-formaldehyde-cobalt adhesion system has good steel wire extraction performance. Therefore, using rice husk silica white as a filler to prepare the belt layer rubber has certain technical advantages.

[0005] However, the sulfurization rate of the bio-based filler rice husk silica white in the rubber composition is slow, resulting in low production efficiency. The existing conventional method to solve this problem is to add a large amount of vulcanizing agent, but this will cause problems such as the rubber becoming brittle, poor heat resistance, and poor physical properties. At the same time, the bio-based filler rice husk silica white also has problems of heat conduction and low heat generation.

[0006] Therefore, it is very necessary and urgent to research and develop a high bio-based elastomer cord rubber composition to alleviate the poor physical properties, slow sulfurization rate, low efficiency, and heat conduction and low heat generation problems caused by using high bio-based rice husk silica white in the existing bio-based tire cord rubber, and then prepare a tire bio-based belt layer rubber with high adhesion and low heat generation performance.

[0007] In view of this, the present invention is specifically proposed. Summary of the Invention

[0008] The object of the present invention is to provide a high bio-based elastomer cord rubber composition, and the cord rubber prepared from the rubber composition has excellent thermal conductivity, low heat generation, and high fatigue performance, which can fully meet the high adhesion and low heat generation performance requirements of tire cord rubber.

[0009] In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:

[0010] A porous three-phase alloy provided by the present invention is mainly prepared by high-temperature jet of carbon black and natural ore powder;

[0011] The content of silicon dioxide in the natural ore powder is 40 - 60%, and the content of aluminum oxide is 30 - 40%;

[0012] The natural ore powder has a microporous structure, with a specific surface area of 30 - 70 m 2 / g, a pore volume of 0.20 - 0.40 cm 3 / g, the number of pores is 100 million - 300 million per gram, and the D50 particle size is 0.25 - 5 μm.

[0013] Further, the mass ratio of carbon black to natural ore powder is 20 - 80:80 - 20;

[0014] And / or, the carbon black includes at least one of N330, N375, and N326.

[0015] Further, the high-temperature jet includes:

[0016] The suspension of natural ore powder mixed by the jet system is sprayed into the carbon black reaction furnace, and the carbon black reacts with the natural ore powder to form an aluminum-silicon-carbon structure, and through aggregation, an aluminum-silicon-carbon aggregate is formed to obtain the porous three-phase alloy;

[0017] The concentration of the suspension of natural ore powder is 15 - 25 wt.%;

[0018] The spraying flow rate of the suspension of natural ore powder is 4000 - 6000 kg / h;

[0019] The temperature of the reaction is 1000 - 1500 °C.

[0020] An application of the above porous three-phase alloy provided by the present invention in the preparation of a high bio-based elastomer cord rubber composition.

[0021] A high bio-based elastomer cord rubber composition provided by the present invention, the rubber composition includes:

[0022] 100 parts of natural rubber, 5 - 15 parts of porous three-phase alloy, 30 - 60 parts of rice husk silica white carbon black, 3 - 7 parts of silane coupling agent, 8 - 12 parts of zinc oxide; 3 - 5 parts of anti-aging agent; 0.75 - 1.5 parts of cobalt salt; 3 - 5 parts of methylene donor; 1 - 2.5 parts of methylene acceptor; 4 - 7 parts of insoluble sulfur; 0.8 - 1.5 parts of accelerator; 0.05 - 0.5 parts of deep eutectic solvent.

[0023] Further, the deep eutectic solvent is mainly prepared from choline chloride and thiourea;

[0024] The molar ratio of choline chloride to thiourea is (1-3):(3-6), preferably 1:3.

[0025] Further, the specific surface area of the rice husk white carbon black is 165-240 m 2 / g, and the particle size is 0.8-7.8 μm;

[0026] And / or, the silane coupling agent includes at least one of TESPT, Si75 and Si747;

[0027] And / or, the accelerator includes at least one of CZ, NS, and DTDM;

[0028] And / or, the antioxidant includes at least one of 4020, RD, and DTPD;

[0029] And / or, the methylene donor includes at least one of melamine resin, melamine formaldehyde resin or hexamethoxymethylmelamine;

[0030] And / or, the methylene acceptor is at least one of phenolic resin and m-cresol formaldehyde adhesive resin.

[0031] A high bio-based elastomer cord rubber provided by the present invention, and the cord rubber is mainly obtained by mixing the above-mentioned high bio-based elastomer cord rubber composition.

[0032] Further, the mixing method includes the following steps:

[0033] According to the mass ratio, natural rubber, porous three-phase alloy, rice husk white carbon black, silane coupling agent, zinc oxide and antioxidant are mixed and then subjected to the first mixing to obtain a mixed rubber A; subsequently, cobalt salt and methylene acceptor are added to the mixed rubber A for the second mixing to obtain a mixed rubber B;

[0034] Then, the methylene donor, insoluble sulfur, accelerator and eutectic solvent are added to the mixed rubber B for the third mixing to obtain the high bio-based elastomer cord rubber.

[0035] Further, the first mixing includes: mixing at a rotation speed of 45-55 rpm for 30-50 s, and then performing plug lifting and plug pressing mixing for 20-30 s until the discharge temperature reaches 140-155 °C;

[0036] And / or, the second mixing includes: mixing at a rotation speed of 25-35 rpm for 30-50 s, and then performing plug lifting and plug pressing mixing for 20-30 s until the discharge temperature reaches 135-145 °C;

[0037] And / or, the third mixing includes: mixing at a rotation speed of 25 - 35 rpm for 30 - 50 s, and then performing plug lifting and plug pressing mixing for 20 - 30 s until the rubber is discharged at 95 - 112 °C.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] The porous three-phase alloy provided by the present invention is mainly prepared by high-temperature jet of carbon black and natural ore powder. The content of silicon dioxide in the natural ore powder is 40 - 60%, and the content of aluminum oxide is 30 - 40%. It has a rich microporous structure and can form a porous structure alloy material (porous three-phase alloy) of aluminum-silicon-carbon aggregates after high-temperature jet treatment. When this porous three-phase alloy is used in high bio-based elastomer cord rubber, it can effectively improve the heat conduction and low heat generation performance of the cord rubber.

[0040] The porous three-phase alloy provided by the present invention can be widely used in the preparation process of high bio-based elastomer cord rubber compositions. The prepared cord rubber has excellent heat conduction, low heat generation and high fatigue performance, and can fully meet the requirements of high adhesion and low heat generation performance of tire cord rubber.

[0041] The high bio-based elastomer cord rubber composition provided by the present invention is mainly prepared by compounding natural rubber, porous three-phase alloy, rice husk silica white carbon black, silane coupling agent, zinc oxide, anti-aging agent, cobalt salt, methylene donor, methylene acceptor, insoluble sulfur, accelerator, and deep eutectic solvent in a specific proportion. In the above rubber composition of the present application, rice husk silica white carbon black is used to replace highly dispersed white carbon black. It not only has the characteristics of high bio-based rubber materials, but also significantly improves the adhesion performance of the rubber compound. Further, the addition of the porous three-phase alloy in the above rubber composition effectively solves the problems of heat conduction and low heat generation of rice husk silica white carbon black. The addition of the deep eutectic solvent effectively alleviates the problems of poor physical properties, slow sulfur vulcanization speed and low efficiency of high bio-based rice husk silica white carbon black in the preparation of tire cord rubber. Therefore, the cord rubber prepared from the high bio-based elastomer cord rubber composition of the present application has excellent heat conduction, low heat generation and high fatigue performance, and can fully meet the requirements of high adhesion and low heat generation performance of tire cord rubber. Detailed Embodiments

[0042] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0043] According to one aspect of the present invention, a porous three-phase alloy is mainly prepared by high-temperature jet of carbon black and natural ore powder;

[0044] The content of silicon dioxide in the natural ore powder is 40 - 60%, and the content of aluminum oxide is 30 - 40%;

[0045] The natural ore powder has a microporous structure, with a specific surface area of 30 - 70 m 2 / g, a pore volume of 0.20 - 0.40 cm 3 / g, the number of pores is 100 million - 300 million per gram, and the D50 particle size is 0.25 - 5 μm.

[0046] The porous three-phase alloy provided by the present invention is mainly prepared by high-temperature jet of carbon black and natural ore powder. The content of silicon dioxide in the natural ore powder is 40 - 60%, and the content of aluminum oxide is 30 - 40%. It has a rich microporous structure. After high-temperature jet treatment, it can aggregate to form a porous structure alloy material (porous three-phase alloy) of aluminum-silicon-carbon aggregates. Using this porous three-phase alloy in high bio-based elastomer cord rubber can effectively improve the heat conduction and low heat generation performance of the cord rubber, and then prepare a tire bio-based belt layer rubber with high adhesion and low heat generation performance.

[0047] In a preferred embodiment of the present invention, the mass ratio of carbon black to natural ore powder is 20 - 80:80 - 20;

[0048] In a preferred embodiment of the present invention, the carbon black includes at least one of N330, N375, and N326.

[0049] In a preferred embodiment of the present invention, the high-temperature jet includes:

[0050] The suspension of natural ore powder mixed by the jet system is sprayed into the carbon black reaction furnace. The carbon black reacts with the natural ore powder to form an aluminum-silicon-carbon structure, and through aggregation, aluminum-silicon-carbon aggregates are obtained to obtain the porous three-phase alloy;

[0051] The concentration of the suspension of natural ore powder is 15 - 25 wt%;

[0052] The spraying flow rate of the suspension of natural ore powder is 4000 - 6000 kg / h;

[0053] The temperature of the reaction is 1000 - 1500 °C.

[0054] According to one aspect of the present invention, an application of the above porous three-phase alloy in the preparation of a high bio-based elastomer cord rubber composition.

[0055] The porous three-phase alloy provided by the present invention can be widely used in the preparation process of high bio-based elastomer carcass ply rubber compositions.

[0056] According to one aspect of the present invention, a high bio-based elastomer carcass ply rubber composition, the rubber composition comprising:

[0057] 100 parts of natural rubber, 5 - 15 parts of porous three-phase alloy, 30 - 60 parts of rice husk precipitated silica, 3 - 7 parts of silane coupling agent, 8 - 12 parts of zinc oxide; 3 - 5 parts of antioxidant; 0.75 - 1.5 parts of cobalt salt; 3 - 5 parts of methylene donor; 1 - 2.5 parts of methylene acceptor; 4 - 7 parts of insoluble sulfur; 0.8 - 1.5 parts of accelerator; 0.05 - 0.5 parts of deep eutectic solvent.

[0058] The high bio-based elastomer carcass ply rubber composition provided by the present invention is mainly obtained by compounding natural rubber, porous three-phase alloy, rice husk precipitated silica, silane coupling agent, zinc oxide, antioxidant, cobalt salt, methylene donor, methylene acceptor, insoluble sulfur, accelerator, and deep eutectic solvent in specific proportions. In the above rubber composition of the present application, rice husk precipitated silica is used to replace highly dispersed precipitated silica, which not only has the characteristics of high bio-based rubber materials, but also significantly improves the adhesion performance of the rubber compound; further, the addition of the porous three-phase alloy in the above rubber composition effectively solves the problems of heat conduction and low heat generation of rice husk precipitated silica; the addition of the deep eutectic solvent effectively alleviates the problems of poor physical properties, slow sulfur vulcanization rate, and low efficiency of high bio-based rice husk precipitated silica in the preparation of tire carcass ply rubber layer. Therefore, the carcass ply rubber prepared from the high bio-based elastomer carcass ply rubber composition of the present application has excellent heat conduction, low heat generation, and high fatigue performance, and can fully meet the requirements of high adhesion and low heat generation performance of tire carcass ply rubber.

[0059] At the same time, it should be noted that the methylene donor and methylene acceptor provide resin crosslinking, enhancing the crosslinking density of the adhesion layer between the rubber and the steel wire surface and enhancing the adhesion strength between the rubber and the steel wire.

[0060] Zinc oxide forms an oxide film on the surface of the steel wire, increasing the surface roughness of the steel wire and enhancing the combination between the rubber and the steel wire; secondly, zinc oxide participates in the vulcanization reaction, enhancing the crosslinking of the rubber and further enhancing the adhesion between the rubber and the steel wire;

[0061] Cobalt salts play a crucial role in the adhesion between rubber and steel, mainly reflected in the following aspects: 1. Cobalt ions in cobalt salts play a key role in the rubber vulcanization process. It promotes the formation of a new material layer between rubber and steel, especially metal sulfide layers (such as copper sulfide CuxS and zinc sulfide ZnS). These sulfide layers enhance the adhesion between rubber and steel. Cobalt ions can accelerate the chemical reaction between rubber and steel, form stable chemical bonds, and thus significantly improve the adhesion strength. 2. The addition of cobalt salts can accelerate the vulcanization reaction, enabling rubber products to reach the required physical properties faster.

[0062] It should be noted that the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned porous three-phase alloy are: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned rice husk silica white carbon black are: 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, and 60 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned silane coupling agent are: 3 parts, 4 parts, 5 parts, and 7 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned zinc oxide are: 8 parts, 9 parts, 10 parts, 11 parts, and 12 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned anti-aging agent are: 3 parts, 4 parts, and 5 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned cobalt salt are: 0.75 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.2 parts, and 1.5 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned methylene donor are: 3 parts, 4 parts, and 5 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned methylene acceptor are: 1 part, 1.5 parts, 1.8 parts, 2.0 parts, 2.3 parts, and 2.5 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned insoluble sulfur are: 4 parts, 5 parts, 6 parts, and 7 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned accelerator are: 0.8 parts, 0.9 parts, 1.0 parts, 1.2 parts, and 1.5 parts; the typical but non-limiting preferred implementation schemes for the addition amount of the above-mentioned deep eutectic solvent are: 0.05 parts, 0.1 parts, 0.3 parts, 0.4 parts, and 0.5 parts.

[0063] In a preferred implementation manner of the present invention, the deep eutectic solvent is mainly prepared from choline chloride and thiourea;

[0064] The molar ratio of choline chloride to thiourea is (1~3):(3~6), preferably 1:3.

[0065] It should be noted that the eutectic solvent is prepared from choline chloride and thiourea, and the specific method is as follows:

[0066] In a reaction kettle made of fluorinated ceramics, stirring is carried out with a tetrafluoro stirrer, and the reaction is carried out at a water bath reaction temperature of 90 - 100 °C for 1 - 4 h. After the reaction is completed, it is put into a plastic container, and then granulation is carried out.

[0067] In a preferred embodiment of the present invention, the specific surface area of the rice husk grayish - white carbon black is 165 - 240 m 2 / g, and the particle size is 0.8 - 7.8 μm;

[0068] In a preferred embodiment of the present invention, the silane coupling agent includes at least one of TESPT, Si75, and Si747;

[0069] In a preferred embodiment of the present invention, the accelerator includes at least one of CZ, NS, and DTDM;

[0070] In a preferred embodiment of the present invention, the anti - aging agent includes at least one of 4020, RD, and DTPD;

[0071] In a preferred embodiment of the present invention, the methylene donor includes at least one of melamine resin, melamine - formaldehyde resin, and hexamethoxymethylmelamine;

[0072] In a preferred embodiment of the present invention, the methylene acceptor is at least one of phenolic resin and m - cresol formaldehyde adhesive resin.

[0073] According to one aspect of the present invention, a high bio - based elastomer cord rubber, the cord rubber is mainly obtained by mixing the above - mentioned high bio - based elastomer cord rubber composition.

[0074] In a preferred embodiment of the present invention, the mixing method includes the following steps:

[0075] According to the mass ratio, natural rubber, porous three - phase alloy, rice husk grayish - white carbon black, silane coupling agent, zinc oxide, and anti - aging agent are mixed and then subjected to the first mixing to obtain a mixed rubber A; subsequently, cobalt salt and methylene acceptor are added to the mixed rubber A for the second mixing to obtain a mixed rubber B;

[0076] Then, methylene donor, insoluble sulfur, accelerator, and eutectic solvent are added to the mixed rubber B for the third mixing to obtain the high bio - based elastomer cord rubber.

[0077] In a preferred embodiment of the present invention, the first kneading includes: kneading at a rotational speed of 45 - 55 rpm for 30 - 50 s, and then performing plug-lifting and plug-pressing kneading for 20 - 30 s until discharging at 140 - 155 °C;

[0078] As a preferred embodiment, in the above first kneading, the typically but non-limitingly preferred implementation schemes for the kneading rotational speed are: 40 rpm, 42 rpm, 44 rpm, 46 rpm, 48 rpm, 50 rpm, 52 rpm, 54 rpm, and 55 rpm; the typically but non-limitingly preferred implementation schemes for the kneading time are: 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 s, 50 s; the typically but non-limitingly preferred implementation schemes for the plug-lifting and plug-pressing kneading time are: 20 s, 22 s, 24 s, 26 s, 28 s, 30 s; the typically but non-limitingly preferred implementation schemes for the discharging temperature of the plug-lifting and plug-pressing kneading are: 140 °C, 141 °C, 142 °C, 143 °C, 144 °C, 145 °C, 146 °C, 147 °C, 148 °C, 149 °C, 150 °C, 151 °C, 152 °C, 153 °C, 154 °C, 155 °C.

[0079] In a preferred embodiment of the present invention, the second kneading includes: kneading at a rotational speed of 25 - 35 rpm for 30 - 50 s, and then performing plug-lifting and plug-pressing kneading for 20 - 30 s until discharging at 135 - 145 °C;

[0080] As a preferred embodiment, in the above second kneading, the typically but non-limitingly preferred implementation schemes for the kneading rotational speed are: 25 rpm, 26 rpm, 27 rpm, 28 rpm, 29 rpm, 30 rpm, 31 rpm, 35 rmp, 33 rmp, 34 rpm, and 35 rpm; the typically but non-limitingly preferred implementation schemes for the kneading time are: 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 s, 50 s; the typically but non-limitingly preferred implementation schemes for the plug-lifting and plug-pressing kneading time are: 20 s, 22 s, 24 s, 26 s, 28 s, 30 s; the typically but non-limitingly preferred implementation schemes for the discharging temperature of the plug-lifting and plug-pressing kneading are: 135 °C, 136 °C, 137 °C, 138 °C, 139 °C, 140 °C, 141 °C, 142 °C, 143 °C, 144 °C, 145 °C.

[0081] In a preferred embodiment of the present invention, the third kneading includes: kneading at a rotational speed of 25 - 35 rpm for 30 - 50 s, and then performing plug-lifting and plug-pressing kneading for 20 - 30 s until discharging at 95 - 112 °C.

[0082] As a preferred embodiment, in the above-mentioned third mixing, the typically but non-limitingly preferred embodiments of the mixing rotation speed are: 25 rpm, 26 rpm, 27 rpm, 28 rpm, 29 rpm, 30 rpm, 31 rpm, 35 rmp, 33 rmp, 34 rpm, and 35 rpm; the typically but non-limitingly preferred embodiments of the mixing time are: 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 s, 50 s; the typically but non-limitingly preferred embodiments of the kneading time of lifting and pressing the plug are: 20 s, 22 s, 24 s, 26 s, 28 s, 30 s; the typically but non-limitingly preferred embodiments of the discharge temperature of the kneading of lifting and pressing the plug are: 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C.

[0083] The technical solution of the present invention will be further described below in conjunction with embodiments.

[0084] Example 1

[0085] A porous three-phase alloy, the preparation method of the porous three-phase alloy includes:

[0086] (1) Raw material preparation:

[0087] Carbon black N330;

[0088] Natural ore powder, the content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%; the natural ore powder has a microporous structure, the specific surface area is 30-70 m 2 / g, the pore volume is 0.20-0.40 cm 3 / g, the number of pores is 100 million - 300 million per gram, and the D50 particle size is 0.25-5 μm.

[0089] (2) High-temperature jet:

[0090] Step 1): The crude oil formula selects a low-moisture raw material oil (coal tar) with a moisture content ≤ 2.0%; the raw material oil is mixed with a high-temperature combustion gas flow above 1200-1800 °C in the reaction furnace section to fully crack the crude oil into carbon black primary particles;

[0091] Step 2): Through the powder jet technology, the porous inorganic material natural ore powder is mixed with process water to obtain a natural ore powder suspension, and then sprayed into the carbon black reaction furnace;

[0092] The concentration of the natural ore powder suspension is 20 wt.%, and the spraying flow rate of the natural ore powder suspension is 5000 kg / h;

[0093] The mass ratio of the carbon black to the natural ore powder is 50:50.

[0094] The specific preparation method is as follows:

[0095] In the jet system, through the powder injection technology, the natural ore powder is mixed evenly with process water, and the concentration of the natural ore powder suspension is controlled to be 20 wt.%. Then, the natural ore powder suspension is sprayed into the carbon black reaction furnace by the jet system, and the spraying flow rate is 5000 kg / h. The mass ratio of the carbon black to the natural ore powder is controlled, and the temperature in the carbon black reaction furnace is set at 1000 °C. The carbon black reacts with the natural ore powder to form an aluminum-silicon-carbon structure, and through aggregation, an aluminum-silicon-carbon aggregate is formed to obtain the porous three-phase alloy.

[0096] Silicon and aluminum atoms of the natural ore powder chemically combine with the carbon black primary particles at high temperature to form -Si-C-Al-, -Si-O-C-O-Al- and -Al-O-Si-O-C- short chain structures; the powder jet technology is that the silicon lattice powder is transported to the precision quantitative interlocking double helix through the mechanical arch breaking, air flow arch breaking devices in the storage bin and the plow blade stirring device at the lower part of the bin. The silicon lattice powder metered by the weighing system and the precision quantitative helix enters the mass transfer cavity of the high-speed jet mixer and is instantaneously mixed with the jet carrier, i.e., process water. The natural ore powder is forced to be dispersed into the jet carrier during the movement process and is quickly diffused into a uniform suspension through the pressure change in the diffuser at the tail of the jet device and is transported to the pressure atomization system;

[0097] Step 3): Through the aggregation of carbon black, a three-phase alloy carbon black aggregate is formed;

[0098] Step 4): The carbon black flue gas is collected and separated by the main bag filter, and the separated tail gas is used for heating the tail gas furnace and power generation of the boiler, and the carbon black is stored after granulation and drying.

[0099] Examples 2 to 5

[0100] A porous three-phase alloy, and the preparation method of the porous three-phase alloy includes:

[0101] (1) Raw material preparation: The same as in Example 1;

[0102] (2) High-temperature jet:

[0103] Step 1): The same as in Example 1;

[0104] Step 2): In Examples 2 to 5, except for the mass ratio of the carbon black to the natural ore powder, the others are the same as in Example 1;

[0105] The mass ratio of the carbon black to the natural ore powder is shown in Table 1.

[0106] Table 1:

[0107]

[0108] Step 3): The same as Example 1;

[0109] Step 4): The same as Example 1.

[0110] Examples 6 - 8

[0111] A high bio - based elastomer cord compound rubber composition, for the composition of the rubber composition, see Table 2.

[0112] Table 2:

[0113]

[0114] The eutectic solvent is prepared from choline chloride and thiourea, and the molar ratio of choline chloride to thiourea is 2:4;

[0115] The specific method includes: In a ceramic reaction kettle, stir with a tetrafluoro stirrer, react at a water bath reaction temperature of 90 - 100 °C for 1 - 4 h, after the reaction, put it into a plastic container, and then granulate.

[0116] The cord compound rubber is prepared by mixing the cord compound rubber composition, and the specific method includes:

[0117] First - stage masterbatch: Start the internal mixer, set the rotation speed at 50 revolutions, first add natural rubber, porous three - phase alloy, rice husk white carbon black, silane coupling agent, zinc oxide and antioxidant, mix for 40 seconds, lift and press the ram for 25 seconds, lift and press the ram until discharging at 150 °C to obtain masterbatch 1;

[0118] Second - stage masterbatch: Start the internal mixer, set the rotation speed at 30 revolutions, first add masterbatch 1, cobalt salt, methylene acceptor, mix for 40 seconds, lift and press the ram for 25 seconds, lift and press the ram until discharging at 140 °C to obtain masterbatch 2;

[0119] Vulcanization: Start the internal mixer, set the rotation speed at 30 revolutions, first add masterbatch 2, methylene donor, insoluble sulfur, accelerator and eutectic solvent, mix for 40 seconds, lift and press the ram for 25 seconds, lift and press the ram until discharging at 100 °C to obtain the cord compound rubber.

[0120] Example 9

[0121] In this example, except for using the porous three - phase alloy prepared in Example 2 to replace the porous three - phase alloy prepared in Example 1, the rest is the same as Example 6.

[0122] Example 10

[0123] In this embodiment, except that the porous three-phase alloy prepared in Example 3 is used to replace the porous three-phase alloy prepared in Example 1, the rest is the same as in Example 6.

[0124] Example 11

[0125] In this embodiment, except that the porous three-phase alloy prepared in Example 4 is used to replace the porous three-phase alloy prepared in Example 1, the rest is the same as in Example 6.

[0126] Example 12

[0127] In this embodiment, except that the porous three-phase alloy prepared in Example 5 is used to replace the porous three-phase alloy prepared in Example 1, the rest is the same as in Example 6.

[0128] Test Example 1

[0129] To demonstrate that the high bio-based elastomer carcass ply rubber composition of the present application can effectively alleviate the problems of poor physical properties, slow sulfur vulcanization speed, and low efficiency caused by the use of high bio-based rice husk silica in existing bio-based tires; and the problems of heat conduction and low heat build-up existing in the bio-based filler rice husk silica. The high bio-based elastomer carcass ply rubber compositions prepared in Examples 6 to 12 are now used for testing, and the specific results are shown in Tables 3 and 4 below.

[0130] Table 3:

[0131]

[0132] Note: In Table 3, when the sulfur vulcanization test conditions are 140 °C * 60 min, MH is the maximum torque; ML is the minimum torque; Ts2 is the time corresponding to (minimum torque + 0.2 Nm); T10 is the time corresponding to (minimum torque + (maximum torque - minimum torque) × 0.1), also known as the scorch time; T30 is the time corresponding to (minimum torque + (maximum torque - minimum torque) × 0.3); T60 is the time corresponding to (minimum torque + (maximum torque - minimum torque) × 0.6); T90 is the time corresponding to (minimum torque + (maximum torque - minimum torque) × 0.9), also known as the optimum vulcanization time. Rev97 is the reversion vulcanization time; M300 is the 300% modulus at 100% elongation of the vulcanized rubber; TB is the tensile strength of the vulcanized rubber; tanδ / 60 °C is the loss factor at 60 °C.

[0133] It should be noted that the meanings of the test items in the test result tables in Test Examples 1 to 4 below are the same as those in Table 3.

[0134] Table 4:

[0135]

[0136] As can be seen from Table 3 and Table 4 above, the cord rubber composition prepared in Examples 6 to 10 (the porous three-phase alloy prepared with the ratio of carbon black to natural ore powder in the range of 20 to 80:80 to 20) has better heat conduction and low heat generation effects.

[0137] For the porous three-phase alloy of the cord rubber composition in Examples 11 and 12, the mass ratio of carbon black to natural ore powder is not within the range of 20 to 80:80 to 20. The reinforcing effect of the prepared rubber composition becomes poor. It can be seen from Example 11 that the TB decreases and the heat generation increases compared with Example 6.

[0138] Example 13

[0139] This example is the same as Example 6 except that the molar ratio of choline chloride to thiourea in the deep eutectic solvent is 1:3.

[0140] Example 14

[0141] This example is the same as Example 6 except that the molar ratio of choline chloride to thiourea in the deep eutectic solvent is 3:6.

[0142] Example 15

[0143] This example is the same as Example 6 except that the molar ratio of choline chloride to thiourea in the deep eutectic solvent is 4:3.

[0144] Example 16

[0145] This example is the same as Example 6 except that the molar ratio of choline chloride to thiourea in the deep eutectic solvent is 5:3.

[0146] Example 17

[0147] This example is the same as Example 6 except that the molar ratio of choline chloride to thiourea in the deep eutectic solvent is 1:8.

[0148] Test Example 2

[0149] To show that the raw material composition of the deep eutectic solvent has a significant impact on the performance of the cord rubber composition of the present application. Now, the cord rubber compositions prepared in Examples 13 to 17 are used for detection, and the specific results are shown in Table 5 below.

[0150] Table 5:

[0151]

[0152] As can be seen from Table 5 above, the technical effects of the cord rubber compositions prepared in Examples 13 and 14 are similar to those of Example 6, and the technical effects of the cord rubber composition of the present application can be achieved.

[0153] However, for the embodiments 15 to 17 where the composition of the eutectic solvent in the cord rubber composition is not within the range of "the molar ratio of choline chloride to thiourea is (1 to 3):(3 to 6)" in this application, the effect of improving the sulfur vulcanization rate of the cord rubber composition is not obvious. That is to say, only the eutectic solvent prepared within the range of "the molar ratio of choline chloride to thiourea is (1 to 3):(3 to 6)" in this application can effectively alleviate the problems of poor physical properties, slow sulfur vulcanization rate, and low efficiency of high bio-based rice husk silica in the preparation of the tire cord rubber layer.

[0154] Example 18

[0155] In this example, except that the mixing process parameters of the cord rubber composition are different from those in Example 1, the rest are the same as in Example 1;

[0156] The mixing method of the cord rubber composition includes:

[0157] First-stage masterbatch: Start the internal mixer, set the rotation speed to 45 revolutions, first add natural rubber, porous three-phase alloy, rice husk silica, silane coupling agent, zinc oxide and antioxidant, mix for 50 seconds, lift and press the ram for 20 seconds, and discharge the rubber at 140 °C after lifting and pressing the ram to obtain masterbatch 1;

[0158] Second-stage masterbatch: Start the internal mixer, set the rotation speed to 25 revolutions, first add masterbatch 1, cobalt salt, methylene acceptor, mix for 50 seconds, lift and press the ram for 20 seconds, and discharge the rubber at 145 °C after lifting and pressing the ram to obtain masterbatch 2;

[0159] Sulfur addition: Start the internal mixer, set the rotation speed to 25 revolutions, first add masterbatch 2, methylene donor, insoluble sulfur, accelerator and eutectic solvent, mix for 50 seconds, lift and press the ram for 20 seconds, and discharge the rubber at 95 °C after lifting and pressing the ram to obtain cord rubber.

[0160] Example 19

[0161] In this example, except that the mixing process parameters of the cord rubber composition are different from those in Example 1, the rest are the same as in Example 1;

[0162] The mixing method of the cord rubber composition includes:

[0163] First-stage masterbatch: Start the internal mixer, set the rotation speed to 55 revolutions, first add natural rubber, porous three-phase alloy, rice husk silica, silane coupling agent, zinc oxide and antioxidant, mix for 30 seconds, lift and press the ram for 30 seconds, and discharge the rubber at 155 °C after lifting and pressing the ram to obtain masterbatch 1;

[0164] Second-stage masterbatch: Start the internal mixer, set the rotation speed to 35 revolutions, first add masterbatch 1, cobalt salt, methylene acceptor, mix for 30 seconds, lift and press the ram for 30 seconds, and discharge the rubber at 135 °C after lifting and pressing the ram to obtain masterbatch 2;

[0165] Vulcanization: Start the internal mixer, set the rotation speed to 35 revolutions, first add the masterbatch 2, methylene donor, insoluble sulfur, accelerator and eutectic solvent, knead for 30 seconds, lift and press the ram for 30 seconds, and lift and press the ram until the discharge temperature reaches 112 °C to obtain the cord rubber.

[0166] Test Example 3

[0167] To show that the kneading method of the cord rubber composition of the present application has a significant impact on the performance of the cord rubber composition of the present application. Now, the cord rubbers prepared in Examples 18 and 19 are used for testing, and the specific results are shown in Table 6 below.

[0168] Table 6:

[0169]

[0170] As can be seen from Table 6 above, under the kneading method of the present application, the heat conduction problem can be effectively solved, and the heat generation also decreases slightly.

[0171] Comparative Examples 1 - 3

[0172] A high bio - based elastomer cord rubber composition, and the composition of the rubber composition is shown in Table 7:

[0173] Table 7:

[0174]

[0175] For the kneading methods of the cord rubber compositions in the above comparative examples, refer to the method of Example 2.

[0176] Comparative Example 4

[0177] This comparative example is the same as Example 2 except that it does not contain "porous three - phase alloy".

[0178] Comparative Example 5

[0179] This comparative example is the same as Example 2 except that it does not contain "eutectic solvent".

[0180] Comparative Example 6

[0181] This comparative example is the same as Example 2 except that it does not contain "methylene donor, methylene acceptor".

[0182] Comparative Example 7

[0183] This comparative example is the same as Example 2 except that rice husk ash carbon black is replaced with carbon black N375 in equal amount.

[0184] Test Example 4

[0185] To demonstrate that the high bio-based elastomer carcass ply rubber composition of the present application can effectively alleviate the problems of poor physical properties, slow sulfur vulcanization speed, and low efficiency caused by the use of high bio-based rice husk silica in existing bio-based tires; as well as the problems of heat conduction and low heat build-up existing in the bio-based filler rice husk silica. The carcass ply rubber prepared using Comparative Examples 1 to 7 is now tested, and the specific results are shown in Tables 8 and 9 below:

[0186] Table 8:

[0187]

[0188] Table 9:

[0189]

[0190] From Tables 8 and 9 above, it can be seen from Comparative Examples 1 to 3 that the sulfur vulcanization speed of rice husk silica is slow, the thermal conductivity is low, and the heat build-up is low. The use of porous three-phase alloy can greatly improve the thermal conductivity; the adhesion of rice husk silica is improved; by comparing Comparative Example 2 with Examples 2 to 6, it can be seen that adding the eutectic solvent can well adjust the sulfur vulcanization speed and the MH hardly changes. Compared with Examples 2 to 6, the implementation mode of Comparative Example 4 without "porous three-phase alloy" shows a significant decrease in thermal conductivity, a decrease in modulus at a specified elongation, and a decrease in MH; compared with Examples 2 to 6, the implementation mode of Comparative Example 5 without "eutectic solvent" shows a significantly slower sulfur vulcanization speed; compared with Examples 2 to 6, the implementation mode of Comparative Example 6 without "methylene donor, methylene acceptor" shows a decrease in MH and a significant decrease in adhesion strength; compared with Examples 2 to 6, the implementation mode of Comparative Example 7 with the equivalent replacement of rice husk ash silica with carbon black N375 shows an increase in MH and a significant increase in heat build-up.

[0191] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high bio-based elastomer cord rubber composition, characterized in that: The rubber composition comprises, by weight: 100 parts of natural rubber, 5-15 parts of porous three-phase alloy, 30-60 parts of rice husk gray carbon black, 3-7 parts of silane coupling agent, 8-12 parts of zinc oxide, 3-5 parts of antioxidant, 0.75-1.5 parts of cobalt salt, 3-5 parts of methylene donor, 1-2.5 parts of methylene acceptor, 4-7 parts of insoluble sulfur, 0.8-1.5 parts of accelerator and 0.05-0.5 parts of deep eutectic solvent; The porous three-phase alloy is mainly prepared by high-temperature jetting of carbon black and natural ore powder; The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%; the natural ore powder has a microporous structure and a specific surface area of ​​30-70m 2 / g, pore volume 0.20~0.40cm 3 / g, the number of pores is 100-300 million / g, and the D50 particle size is 0.25-5μm; The mass ratio of carbon black to natural ore powder in the porous three-phase alloy is 20-80:80-20; The low eutectic solvent is mainly prepared from choline chloride and thiourea, and the molar ratio of choline chloride to thiourea is (1-3): (3-6).

2. The high bio-based elastomer cord rubber composition according to claim 1, characterized in that: The carbon black includes at least one of N330, N375 and N326.

3. The high bio-based elastomer cord rubber composition according to claim 1, characterized in that: The high temperature jet comprises: The natural ore powder suspension mixed by the jet system is sprayed into the carbon black reaction furnace, and the carbon black reacts with the natural ore powder to form an aluminum-silicon-carbon structure, and then forms an aluminum-silicon-carbon aggregate through aggregation to obtain the porous three-phase alloy; The concentration of the natural ore powder suspension is 15-25wt%; The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h; The reaction temperature is 1000-1500°C.

4. The high bio-based elastomer cord rubber composition according to claim 1, characterized in that: The specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm; And / or, the silane coupling agent includes at least one of TESPT, Si75 and Si747; And / or, the accelerator includes at least one of CZ, NS, and DTDM; And / or, the antioxidant includes at least one of 4020, RD, and DTPD; And / or, the methylene donor comprises at least one of melamine resin, melamine formaldehyde resin or hexamethoxymethylmelamine; And / or, the methylene acceptor is at least one of a phenolic resin and a m-cresol formaldehyde adhesive resin.

5. A high bio-based elastomer cord rubber, characterized in that: The tire cord rubber is mainly obtained by mixing the high bio-based elastomer tire cord rubber composition according to any one of claims 1 to 4.

6. The high bio-based elastomer cord rubber according to claim 5, characterized in that: The mixing method comprises the following steps: Natural rubber, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, zinc oxide and antioxidant are mixed according to mass ratio and then kneaded for the first time to obtain rubber mix A; then cobalt salt and methylene acceptor are added to rubber mix A and kneaded for the second time to obtain rubber mix B; Then, the methylene donor, the insoluble sulfur, the accelerator and the low eutectic solvent are added into the rubber compound B for the third mixing to obtain the high bio-based elastomer cord rubber.

7. The high bio-based elastomer cord rubber according to claim 6, characterized in that: The first mixing includes: mixing at a rotation speed of 45-55 rpm for 30-50 seconds, and then mixing with the plug lifting and pressing for 20-30 seconds until the temperature reaches 140-155° C. for debonding; And / or, the second mixing comprises: mixing at a rotation speed of 25-35 rpm for 30-50 seconds, followed by mixing with the plug lifted and pressed for 20-30 seconds until the temperature reaches 135-145° C. for debonding; And / or, the third mixing includes: mixing at a rotation speed of 25-35 rpm for 30-50 seconds, and then mixing by lifting and pressing the plug for 20-30 seconds to 95-112° C. for debonding.

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