Highly bio-based elastomer cushion rubber composition

Abstract

The present invention provides a high-biobased elastomer cushion 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 gray carbon black, silane coupling agent, activator, antioxidant, vulcanizer and low eutectic solvent in a specific proportion. In the above-mentioned rubber composition of the present application, rice husk gray carbon black is used to replace high-dispersion white carbon black, which has the characteristics of a high-biobased rubber material; further, the addition of porous three-phase alloy to the rubber composition effectively solves the problem of poor thermal conductivity of rice husk gray carbon black; by adding a low eutectic solvent, the problem of poor physical properties, slow sulfur rate and low efficiency of high-biobased rice husk gray carbon black in the preparation of tire cushion rubber layer is effectively alleviated. Therefore, the cushion rubber prepared by the high-biobased elastomer cushion rubber composition of the present application has excellent thermal conductivity, low heat generation and high fatigue performance, which can fully meet the preparation requirements of tire cushion rubber.

Description

Technical Field

[0001] The invention relates to the technical field of rubber compositions, in particular to a high-biobased elastomer cushion rubber composition. Background Art

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

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

[0004] However, the existing tire cushion rubber uses bio-based filler rice husk ash white carbon black, but the curing rate is slow, resulting in low production efficiency. The conventional method to solve this problem is to add a large amount of vulcanizing agent, but this will cause the rubber to become brittle, and the heat resistance and physical properties will deteriorate. At the same time, the bio-based filler rice husk ash white carbon black also has the problem of poor thermal conductivity.

[0005] Therefore, it is necessary and urgent to research and develop a high-biobased elastomer cushion rubber composition to alleviate the poor physical properties, slow sulfur rate, low efficiency, and thermal conductivity problems of existing bio-based tire cushion rubber due to the use of high-biobased rice husk gray carbon black.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The object of the present invention is to provide a high bio-based elastomer cushion rubber composition, which can effectively improve the thermal conductivity, low heat generation and fatigue resistance of the cushion rubber.

[0008] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0009] The present invention provides a porous three-phase alloy, wherein the porous three-phase alloy is mainly prepared by high-temperature jet flow of carbon black and natural ore powder;

[0010] The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%;

[0011] The natural mineral 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.

[0012] Furthermore, the mass ratio of the carbon black to the natural ore powder is 20~80:80~20;

[0013] Preferably, the carbon black includes at least one of N330, N375, and N326.

[0014] Furthermore, the high temperature jet comprises:

[0015] 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;

[0016] The concentration of the natural ore powder suspension is 15-25wt.%;

[0017] The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h;

[0018] The reaction temperature is 1000~1500℃.

[0019] The present invention provides an application of the porous three-phase alloy in the preparation of a high-biobased elastomer cushion rubber composition.

[0020] The present invention provides a high-biobased elastomer cushion rubber composition, the rubber composition comprising:

[0021] 100 parts of natural rubber, 5-15 parts of porous three-phase alloy, 25-40 parts of rice husk ash white carbon black, 1.5-4 parts of silane coupling agent, 3-6 parts of activator, 2-5 parts of antioxidant, 3-6 parts of vulcanizing agent and 0.2-0.5 parts of low eutectic solvent.

[0022] Furthermore, the deep eutectic solvent is mainly prepared from zinc chloride, choline chloride and thiourea;

[0023] Preferably, the molar ratio of zinc chloride, choline chloride and thiourea is (1-3):(1-3):(3-6).

[0024] Furthermore, the specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm;

[0025] And / or, the silane coupling agent includes at least one of TESPT, Si75, OTES and Si747;

[0026] And / or, the activator comprises at least one of TPZ, zinc oxide, and stearic acid;

[0027] And / or, the antioxidant includes at least one of antioxidant 4020, antioxidant 4010NA, and antioxidant RD;

[0028] And / or, the vulcanizing agent includes at least one of insoluble sulfur HDOT-20 and oil-extended sulfur.

[0029] The present invention provides a high-biobased elastomer cushion rubber, which is mainly obtained by mixing the above-mentioned high-biobased elastomer cushion rubber composition.

[0030] Further, the mixing method comprises the following steps:

[0031] Natural rubber, porous three-phase alloy, rice husk ash white carbon black, silane coupling agent, activator and antioxidant are mixed according to mass ratio and then kneaded for the first time to obtain rubber mix A, and then kneaded for the second time to obtain rubber mix B;

[0032] Then, the vulcanizing agent and the low eutectic solvent are added into the rubber mix B for the third mixing to obtain the cushion rubber.

[0033] Furthermore, the first mixing includes: mixing at a rotation speed of 45-55 rpm for 30-50 seconds, and then mixing at a temperature of 140-155° C. for 20-30 seconds by lifting and pressing the plug;

[0034] And / or, the second mixing comprises: mixing at a rotation speed of 25-35 rpm for 30-50 seconds, and then mixing with the plug lifting and pressing for 20-30 seconds until the temperature reaches 135-145° C. for debonding;

[0035] And / or, the third mixing includes: mixing at a rotation speed of 25-35 rpm for 30-50 seconds, and then mixing with the plug lifting and pressing for 20-30 seconds to 95-110° C. for debonding.

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

[0037] The porous three-phase alloy provided by the present invention is mainly prepared by high-temperature jetting of carbon black and natural ore powder. The natural ore powder has a silicon dioxide content of 40-60%, an aluminum oxide content of 30-40%, and 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. The porous three-phase alloy is used in a high-biobased elastomer cushion rubber composition, which can effectively improve the thermal conductivity, low heat generation and high fatigue performance of the cushion rubber. DETAILED DESCRIPTION

[0038] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] According to one aspect of the present invention, a porous three-phase alloy is prepared mainly from carbon black and natural ore powder by high-temperature jet;

[0040] The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%;

[0041] The natural mineral powder has a microporous structure and a specific surface area of ​​30-70 m 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.

[0042] The porous three-phase alloy provided by the present invention is mainly prepared by high-temperature jetting of carbon black and natural ore powder, wherein the content of silicon dioxide in the natural ore powder is 40-60%, the content of aluminum oxide is 30-40%, and the porous three-phase alloy has a rich microporous structure. After high-temperature jetting treatment, the porous three-phase alloy can be aggregated to form a porous structure alloy material (porous three-phase alloy) of aluminum-silicon-carbon aggregates. The porous three-phase alloy is used in a high-biobased elastomer cushion rubber composition, which can effectively improve the thermal conductivity, low heat generation and high fatigue performance of the cushion rubber.

[0043] In a preferred embodiment of the present invention, the mass ratio of the carbon black to the natural ore powder is 20-80:80-20;

[0044] In a preferred embodiment of the present invention, the carbon black includes at least one of N330, N375, and N326.

[0045] In a preferred embodiment of the present invention, the high temperature jet comprises:

[0046] 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;

[0047] The concentration of the natural ore powder suspension is 15-25wt%;

[0048] The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h;

[0049] The reaction temperature is 1000-1500°C.

[0050] According to one aspect of the present invention, the porous three-phase alloy is used in preparing a high bio-based elastomer cushion rubber composition.

[0051] The porous three-phase alloy provided by the invention can be widely used in the preparation process of a high-biobased elastomer cushion rubber composition.

[0052] According to one aspect of the present invention, a high bio-based elastomer cushion rubber composition comprises:

[0053] 100 parts of natural rubber, 5-15 parts of porous three-phase alloy, 25-40 parts of rice husk ash white carbon black, 1.5-4 parts of silane coupling agent, 3-6 parts of activator, 2-5 parts of antioxidant, 3-6 parts of vulcanizing agent and 0.2-0.5 parts of low eutectic solvent.

[0054] The high-biobased elastomer cushion rubber composition provided by the present invention is mainly obtained by compounding natural rubber, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, activator, antioxidant, vulcanizing agent and low eutectic solvent in a specific proportion. In the above-mentioned rubber composition of the present application, rice husk gray carbon black is used to replace high-dispersion white carbon black, which has the characteristics of a high-biobased rubber material; further, the addition of porous three-phase alloy to the above-mentioned rubber composition effectively solves the problem of poor thermal conductivity of rice husk gray carbon black; through the addition of low eutectic solvent, the problems of poor physical properties, slow sulfur rate and low efficiency of high-biobased rice husk gray carbon black in the preparation of tire cushion rubber layer are effectively alleviated. Therefore, the cushion rubber prepared by the high-biobased elastomer cushion rubber composition of the present application has excellent thermal conductivity, low heat generation and high fatigue performance, which can fully meet the preparation requirements of tire cushion rubber.

[0055] It should be noted that the typical but non-limiting preferred embodiments of the addition amount of the 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 embodiments of the addition amount of the rice husk gray white carbon black are: 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts and 40 parts; the typical but non-limiting preferred embodiments of the addition amount of the silane coupling agent are: The preferred embodiments of the controllable amount are: 1.5 parts, 2 parts, 3 parts and 4 parts; the typical but non-limiting preferred embodiments of the addition amount of the above-mentioned activator are: 3 parts, 4 parts, 5 parts and 6 parts; the typical but non-limiting preferred embodiments of the addition amount of the above-mentioned antioxidant are: 2 parts, 3 parts, 4 parts and 5 parts; the typical but non-limiting preferred embodiments of the addition amount of the above-mentioned vulcanizing agent are: 3 parts, 4 parts, 5 parts and 6 parts; the typical but non-limiting preferred embodiments of the addition amount of the above-mentioned low eutectic solvent are: 0.2 parts, 0.3 parts, 0.4 parts and 0.5 parts.

[0056] In a preferred embodiment of the present invention, the deep eutectic solvent is mainly prepared from zinc chloride, choline chloride and thiourea;

[0057] Preferably, the molar ratio of zinc chloride, choline chloride and thiourea is (1-3):(1-3):(3-6).

[0058] It should be noted that the deep eutectic solvent is prepared from zinc chloride, choline chloride and thiourea by the following specific method:

[0059] Place the mixture in a water bath at 80-99°C, use a glass flask, and stir with a PTFE stirring rod or a PTFE magnetic rotor. React for 1-4 hours. Add zinc chloride after it becomes liquid. Continue stirring until a transparent liquid is formed. Pour out quickly and spread it evenly in a glass container.

[0060] In a preferred embodiment of the present invention, the specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm;

[0061] In a preferred embodiment of the present invention, the silane coupling agent includes at least one of TESPT, Si75, OTES and Si747;

[0062] In a preferred embodiment of the present invention, the activator comprises at least one of TPZ, zinc oxide, and stearic acid;

[0063] In a preferred embodiment of the present invention, the antioxidant includes at least one of antioxidant 4020, antioxidant 4010NA, and antioxidant RD;

[0064] In a preferred embodiment of the present invention, the vulcanizing agent includes at least one of HDOT-20 and oil-extended sulfur.

[0065] According to one aspect of the present invention, a high bio-based elastomer cushion rubber is provided. The cushion rubber is mainly obtained by mixing the above-mentioned high bio-based elastomer cushion rubber composition.

[0066] In a preferred embodiment of the present invention, the mixing method comprises the following steps:

[0067] Natural rubber, porous three-phase alloy, rice husk ash white carbon black, silane coupling agent, activator and antioxidant are mixed according to mass ratio and then kneaded for the first time to obtain rubber mix A, and then kneaded for the second time to obtain rubber mix B;

[0068] Then, the vulcanizing agent and the low eutectic solvent are added into the rubber mix B for the third mixing to obtain the cushion rubber.

[0069] In a preferred embodiment of the present invention, the first mixing comprises: mixing at a rotation speed of 45-55 rpm for 30-50 seconds, followed by mixing with the bolt raised and pressed for 20-30 seconds until the temperature reaches 140-155° C. for debonding;

[0070] As a preferred embodiment, in the first mixing, the mixing speed is typically but not limited to 40 rpm, 42 rpm, 44 rpm, 46 rpm, 48 rpm, 50 rpm, 52 rpm, 54 rpm and 55 rpm; the mixing time is typically but not limited to 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 ​​s, 50 s; the mixing time of the plug lifting and pressing is typically but not limited to 20 s, 22 s, 24 s, 26 s, 28 s, 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 ​​s, 50 s. s; Typical but non-limiting preferred embodiments of the discharge temperature of the plug-lifting and plug-pressing mixing 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, and 155°C.

[0071] In a preferred embodiment of the present invention, the second mixing comprises: mixing at a rotation speed of 25-35 rpm for 30-50 seconds, and then mixing at a temperature of 135-145° C. for 20-30 seconds by lifting and pressing the plug;

[0072] As a preferred embodiment, in the second mixing, the mixing speed is typically but not limited to 25 rpm, 26 rpm, 27 rpm, 28 rpm, 29 rpm, 30 rpm, 31 rpm, 35 rpm, 33 rpm, 34 rpm and 35 rpm; the mixing time is typically but not limited to 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 ​​s, 50 s; the mixing time of the plug lifting and pressing is typically but not limited to 20 s, 22 s, 24 s, 26 s, 28 s, 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 ​​s, 50 s. s; typical but non-limiting preferred embodiments of the discharge temperature of the plug-pressing mixing are: 135°C, 136°C, 137°C, 138°C, 139°C, 140°C, 141°C, 142°C, 143°C, 144°C, and 145°C.

[0073] In a preferred embodiment of the present invention, the third 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 to 95-110° C. for debonding.

[0074] As a preferred embodiment, in the third mixing, the mixing speed is typically but not limited to 25 rpm, 26 rpm, 27 rpm, 28 rpm, 29 rpm, 30 rpm, 31 rpm, 35 rpm, 33 rpm, 34 rpm and 35 rpm; the mixing time is typically but not limited to 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 ​​s, 50 s; the mixing time of the plug lifting and pressing is typically but not limited to 20 s, 22 s, 24 s, 26 s, 28 s, 30 s, 32 s, 34 s, 36 s, 38 s, 40 s, 42 s, 44 s, 46 s, 48 ​​s, 50 s. s; typical but non-limiting preferred embodiments of the discharge temperature of the plug-pressing mixing are: 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, and 105°C.

[0075] The technical solution of the present invention will be further described below in conjunction with embodiments.

[0076] Example 1

[0077] A porous three-phase alloy, wherein the preparation method of the porous three-phase alloy comprises:

[0078] (1) Raw material preparation:

[0079] Carbon black N330;

[0080] Natural mineral powder, wherein the content of silicon dioxide in the natural mineral powder is 40-60%, and the content of aluminum oxide is 30-40%; the natural mineral powder has a microporous structure, a specific surface area of ​​30-70 m2 / g, a pore volume of 0.20-0.40 cm3 / g, a pore number of 100-300 million / g, and a D50 particle size of 0.25-5 μm.

[0081] (2) High temperature jet:

[0082] Step 1): The crude oil formula uses low-moisture raw oil (coal tar) with a moisture content of ≤2.0%; the raw oil is mixed with a high-temperature combustion airflow above 1200-1800°C in the reactor section to fully crack the crude oil into primary carbon black particles;

[0083] Step 2): By using powder jet technology, the porous inorganic material natural ore powder is mixed with process water to obtain a natural ore powder suspension, which is then sprayed into the carbon black reactor;

[0084] The concentration of the natural ore powder suspension is 20wt.%, and the injection flow rate of the natural ore powder suspension is 5000kg / h;

[0085] The mass ratio of the carbon black to the natural ore powder is 50:50.

[0086] The specific preparation method is as follows:

[0087] In the jet system, the natural ore powder and process water are mixed evenly by powder injection technology, and the concentration of the natural ore powder suspension is controlled to be 20wt.%. The natural ore powder suspension is then sprayed into the carbon black reactor by the jet system, and the injection flow rate is 5000kg / h. The mass ratio of carbon black to natural ore powder is controlled, and the temperature in the carbon black reactor is set to 1000℃. Carbon black reacts with natural ore powder to form an aluminum-silicon-carbon structure, which is aggregated to form an aluminum-silicon-carbon aggregate to obtain the porous three-phase alloy.

[0088] The silicon and aluminum atoms of the natural ore powder are chemically combined with the carbon black primary particles at high temperature to form short chain structures of -Si-C-Al-, -Si-OCO-Al- and -Al-O-Si-OC-; the powder jet technology is that the silicon lattice powder is transported to the precisely quantitative embedded double helix through the mechanical arch breaking device, the airflow arch breaking device and the plow blade stirring device at the bottom of the silo in the storage bin, and the silicon lattice powder measured by the weighing system and the precise quantitative spiral enters the mass transfer cavity of the high-speed jet mixer, and is instantly 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, and is rapidly diffused into a uniform suspension through pressure changes in the diffuser at the tail of the ejector, and is transported to the pressure atomization system;

[0089] Step 3): Forming three-phase alloy carbon black aggregates through the aggregation of carbon black;

[0090] Step 4): The carbon black flue gas is collected and separated by the main bag filter. The separated tail gas is used for tail gas furnace heating and boiler power generation. The carbon black is granulated and dried and then stored.

[0091] Embodiment 2~5

[0092] A porous three-phase alloy, wherein the preparation method of the porous three-phase alloy comprises:

[0093] (1) Raw material preparation: same as in Example 1;

[0094] (2) High temperature jet:

[0095] Step 1): Same as Example 1;

[0096] Step 2): In the embodiments 2 to 5, except for the mass ratio of carbon black to natural ore powder, the rest is the same as that of embodiment 1;

[0097] The mass ratio of the carbon black to the natural ore powder is shown in Table 1.

[0098] Table 1:

[0099]

[0100] Step 3): Same as Example 1;

[0101] Step 4): Same as Example 1.

[0102] Embodiment 6-8

[0103] A high bio-based elastomer cushion rubber composition, the composition of the rubber composition is shown in Table 2.

[0104] Table 2:

[0105]

[0106] The deep eutectic solvent is prepared from zinc chloride, choline chloride and thiourea, and the molar ratio of zinc chloride, choline chloride and thiourea is 2:2:4;

[0107] The specific preparation method of the low eutectic solvent is as follows: add choline chloride and thiourea into a glass flask in a water bath at 80-99° C., stir with a PTFE stirring rod or a PTFE magnetic rotor, react for 3 hours, add zinc chloride after it becomes liquid, continue stirring until a transparent liquid is formed, quickly pour out, and spread evenly in a glass container.

[0108] The cushion rubber composition is mixed to prepare the cushion rubber, and the specific method includes:

[0109] Stage 1 masterbatch: start the internal mixer, set the speed to 50 rpm, first add natural rubber, CNTs, rice husk ash white carbon black, silane coupling agent, activator, antioxidant, mix for 40 seconds, remove the plug and mix for 25 seconds, remove the plug and mix until the temperature reaches 150°C to discharge the glue, and obtain masterbatch 1;

[0110] Second stage masterbatch: start the internal mixer, set the speed to 30 rpm, add masterbatch 1 first, mix for 40 seconds, lift the plug and press the plug to mix for 25 seconds, lift the plug and press the plug to mix until the temperature reaches 140℃ to discharge the glue, and obtain masterbatch 2;

[0111] Vulcanization: Start the internal mixer, set the speed to 30 rpm, first add masterbatch 2, vulcanizing agent, and low eutectic solvent, mix for 40 seconds, lift the plug and press the plug to mix for 25 seconds, lift the plug and press the plug to mix until 100°C to discharge the glue, and obtain the cushion rubber.

[0112] Example 9

[0113] This embodiment is the same as Embodiment 6 except that the porous three-phase alloy prepared in Embodiment 2 is used to replace the porous three-phase alloy prepared in Embodiment 1.

[0114] Example 10

[0115] This embodiment is the same as Embodiment 6 except that the porous three-phase alloy prepared in Embodiment 3 is used to replace the porous three-phase alloy prepared in Embodiment 1.

[0116] Embodiment 11

[0117] This embodiment is the same as Embodiment 6 except that the porous three-phase alloy prepared in Embodiment 4 is used to replace the porous three-phase alloy prepared in Embodiment 1.

[0118] Example 12

[0119] This embodiment is the same as Embodiment 6 except that the porous three-phase alloy prepared in Embodiment 5 is used to replace the porous three-phase alloy prepared in Embodiment 1.

[0120] Test Example 1

[0121] In order to show that the cushion rubber composition of the present application can effectively alleviate the problems of poor physical properties, slow sulfurization rate and low efficiency caused by the use of high-biobased rice husk gray carbon black in existing bio-based tires, as well as the problems of thermal conductivity and low heat generation of bio-based filler rice husk gray carbon black, the cushion rubber prepared in Examples 6 to 12 is now used for testing, and the specific results are shown in Tables 3 and 4 below.

[0122] Table 3:

[0123]

[0124] Note: In Table 3, when the vulcanization test condition is 140℃*60min, MH is the maximum torque; ML is the minimum torque; Ts2 is the time corresponding to (minimum torque + 0.2Nm); 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 positive vulcanization time. Rev97 is the return vulcanization time; M300 is the 300% tensile strength of the vulcanized rubber; TB is the tensile strength of the vulcanized rubber; tanδ / 60℃ is the loss factor at 60℃.

[0125] It should be noted that the meanings of the test items in the test result tables of the following Test Examples 1 to 4 are the same as those in Table 3.

[0126] Table 4:

[0127]

[0128] It can be seen from Tables 3 and 4 above that the cushion rubber compositions prepared in Examples 6 to 10 (porous three-phase alloys prepared with a ratio of carbon black to natural ore powder in the range of 20 to 80:80 to 20) have better thermal conductivity and low heat generation effects.

[0129] However, the mass ratio of carbon black to natural ore powder in the porous three-phase alloy of the cushion rubber composition of Examples 11 and 12 is not within the range of 20-80:80:20, and the reinforcement effect of the prepared rubber composition is poor. It can be seen from Example 11 that TB is reduced and the heat generation is increased compared with Example 6.

[0130] Example 13

[0131] This embodiment is the same as Embodiment 6 except that the molar ratio of zinc chloride, choline chloride and thiourea in the deep eutectic solvent is 1:1:3.

[0132] Embodiment 14

[0133] This embodiment is the same as Embodiment 6 except that the molar ratio of zinc chloride, choline chloride and thiourea in the deep eutectic solvent is 3:3:6.

[0134] Embodiment 15

[0135] This embodiment is the same as Embodiment 6 except that the molar ratio of zinc chloride, choline chloride and thiourea in the deep eutectic solvent is 5:3:6.

[0136] Example 16

[0137] This embodiment is the same as Embodiment 6 except that the molar ratio of zinc chloride, choline chloride and thiourea in the deep eutectic solvent is 3:5:6.

[0138] Embodiment 17

[0139] This embodiment is the same as Embodiment 6 except that the molar ratio of zinc chloride, choline chloride and thiourea in the deep eutectic solvent is 1:1:8.

[0140] Test Example 2

[0141] In order to show that the raw material composition of the low eutectic solvent has a significant effect on the performance of the cushion rubber composition of the present application, the cushion rubber prepared in Examples 13 to 17 is used for testing, and the specific results are shown in Table 5 below.

[0142] Table 5:

[0143]

[0144] It can be seen from Table 5 above that the technical effects of the cushion rubber compositions prepared in Examples 13 and 14 are almost the same as those in Example 6, and the technical effects of the cushion rubber compositions of the present application can be achieved.

[0145] However, the composition of the low eutectic solvent in the cushion rubber composition of Examples 15 to 17 is not within the range of "the molar ratio of zinc chloride, choline chloride and thiourea is (1-3): (1-3): (3-6)" in the present application, and the sulphurization rate improvement effect of the cushion rubber composition is not obvious. In other words, only the low eutectic solvent prepared within the range of "the molar ratio of zinc chloride, choline chloride and thiourea is (1-3): (1-3): (3-6)" in the present application can effectively alleviate the problems of poor physical properties, slow sulphurization rate and low efficiency of high bio-based rice husk gray white carbon black in the preparation of tire cushion rubber layer.

[0146] Embodiment 18

[0147] This embodiment is the same as Embodiment 1 except that the mixing process parameters of the cushion rubber composition are different from those of Embodiment 1;

[0148] The mixing method of the cushion rubber composition comprises:

[0149] Stage 1 masterbatch: start the internal mixer, set the speed to 45 rpm, first add natural rubber, CNTs, rice husk ash white carbon black, silane coupling agent, activator and antioxidant, mix for 50 seconds, remove the plug and mix for 20 seconds, remove the plug and mix until the temperature reaches 140°C to discharge the glue, and obtain masterbatch 1;

[0150] Second stage masterbatch: start the internal mixer, set the speed to 25 rpm, add masterbatch 1 first, mix for 50 seconds, lift the plug and press the plug to mix for 20 seconds, lift the plug and press the plug to mix until the temperature reaches 145°C to discharge the glue, and obtain masterbatch 2;

[0151] Vulcanization: Start the internal mixer, set the speed to 25 rpm, first add masterbatch 2, vulcanizing agent, and low eutectic solvent, mix for 50 seconds, lift the plug and press the plug to mix for 20 seconds, lift the plug and press the plug to mix until the temperature reaches 95°C for rubber discharge to obtain cushion rubber.

[0152] Embodiment 19

[0153] This embodiment is the same as Embodiment 1 except that the mixing process parameters of the cushion rubber composition are different from those of Embodiment 1;

[0154] The mixing method of the cushion rubber composition comprises:

[0155] Stage 1 masterbatch: start the internal mixer, set the speed to 55 rpm, first add natural rubber, CNTs, rice husk ash white carbon black, silane coupling agent, activator and antioxidant, mix for 30 seconds, lift the plug and press the plug to mix for 30 seconds, lift the plug and press the plug to mix until the temperature reaches 155°C to discharge the glue, and obtain masterbatch 1;

[0156] Second stage masterbatch: start the internal mixer, set the speed to 35 rpm, add masterbatch 1 first, mix for 30 seconds, lift the plug and press the plug to mix for 30 seconds, lift the plug and press the plug to mix until the temperature reaches 135℃ to discharge the glue, and obtain masterbatch 2;

[0157] Vulcanization: Start the internal mixer, set the speed to 35 rpm, first add masterbatch 2, vulcanizing agent, and low eutectic solvent, mix for 30 seconds, lift the plug and press the plug to mix for 30 seconds, lift the plug and press the plug to mix until the temperature reaches 110°C for rubber discharge to obtain cushion rubber.

[0158] Test Example 3

[0159] In order to show that the mixing method of the cushion rubber composition of the present application has a significant effect on the performance of the cushion rubber composition of the present application, the cushion rubber prepared in Examples 18 and 19 is used for testing, and the specific results are shown in Table 6 below.

[0160] Table 6:

[0161]

[0162] It can be seen from Table 6 above that the heat conduction problem can be effectively solved under the mixing method of the present application, and the heat generation is also slightly reduced.

[0163] Comparative Examples 1 to 5

[0164] A high bio-based elastomer cushion rubber composition, the composition of the rubber composition is shown in Table 7:

[0165] Table 7:

[0166]

[0167] Note: The difference between Comparative Example 1 and Example 6 is that the deep eutectic solvent is not included;

[0168] The difference between Comparative Example 2 and Example 6 is that it does not contain porous three-phase alloy and eutectic solvent.

[0169] The difference between Comparative Example 3 and Example 6 is that rice husk silica white carbon black is replaced by carbon black N330, and it does not contain porous three-phase alloy, eutectic solvent and silane coupling agent.

[0170] The difference between Comparative Example 4 and Example 6 is that it does not contain porous three-phase alloy.

[0171] The difference between Comparative Example 5 and Example 6 is that only rice husk silica white carbon black is replaced by carbon black N330.

[0172] The mixing method of the above-mentioned comparative example pad rubber compositions refers to the method of Example 6.

[0173] Test Example 4

[0174] To show that the pad rubber composition of the present application can effectively alleviate the problems of poor physical properties, slow sulfur curing speed and low efficiency brought by the existing bio-based tires due to the use of high bio-based rice husk silica white carbon black; and the problems of heat conduction and low heat generation existing in the bio-based filler rice husk silica white carbon black. Now, the pad rubbers prepared from Comparative Examples 1 to 5 are used for detection, and the specific results are shown in Table 8 below:

[0175] Table 8:

[0176]

[0177] It can be seen from Table 8 above that from Comparative Examples 3 to 5, it can be seen that the thermal conductivity significantly decreases when all rice husk silica white carbon black is used. By using porous three-phase alloy in combination, the heat conduction problem can be solved, and the heat generation also slightly decreases; from Comparative Examples 1, 2 and Examples 6 to 8, it can be seen that the use of eutectic solvent can effectively solve the sulfur curing speed problem, and at the same time, MH hardly changes.

[0178] 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 recorded 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 cushion rubber composition, characterized in that: The rubber composition comprises, by weight: 100 parts of natural rubber, 5-15 parts of porous three-phase alloy, 25-40 parts of rice husk gray white carbon black, 1.5-4 parts of silane coupling agent, 3-6 parts of activator, 2-5 parts of antioxidant, 3-6 parts of vulcanizing agent and 0.2-0.5 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 low eutectic solvent is prepared from zinc chloride, choline chloride and thiourea, and the molar ratio of zinc chloride, choline chloride and thiourea is (1-3): (1-3): (3-6).

2. The high bio-based elastomer cushion rubber composition according to claim 1, characterized in that: The mass ratio of the carbon black to the natural ore powder in the porous three-phase alloy is 20-80:80-20.

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

4. The high bio-based elastomer cushion 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.

5. The high bio-based elastomer cushion 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, OTES and Si747; And / or, the activator comprises at least one of TPZ, zinc oxide, and stearic acid; And / or, the antioxidant includes at least one of antioxidant 4020, antioxidant 4010NA, and antioxidant RD; And / or, the vulcanizing agent includes at least one of HDOT-20 and oil-extended sulfur.

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

7. The high bio-based elastomer cushion rubber according to claim 6, characterized in that: The mixing method comprises the following steps: Natural rubber, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, activator and antioxidant are mixed according to mass ratio and then kneaded for the first time to obtain rubber mix A, and then kneaded for the second time to obtain rubber mix B; Then, the vulcanizing agent and the low eutectic solvent are added into the rubber mix B for the third mixing to obtain the cushion rubber.

8. The high bio-based elastomer cushion rubber according to claim 7, 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 with the plug lifting and pressing for 20-30 seconds to 95-110° C. for debonding.

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