Pyrolysis carbon black reinforced tire transition layer rubber material and preparation method thereof

Abstract

The invention relates to a pyrolysis carbon black reinforced tire transition layer rubber material and a preparation method thereof. The pyrolysis carbon black reinforced tire transition layer rubber material comprises the following components in parts by weight: 93.5-97.5 parts of first section rubber; 2-6 parts of sulfur; 0.3 to 0.8 part of an accelerant; and 0.1 to 0.5 part of scorch retarder. The head section rubber comprises the following components in parts by weight: 40-60 parts of natural rubber; 30 to 50 parts of carbon black; 5-15 parts of thermal cracking carbon black; 3-10 parts of zinc oxide; 2-6 parts of an anti-aging agent; and 0.2 to 1 part of cobalt boroacylate. Compared with the prior art, zinc oxide and white carbon black contained in the thermal cracking carbon black are utilized, and on the premise that the tensile property of the tire transition layer rubber material is not reduced, the cord thread drawing force is improved, and the heat generation performance of the tire transition layer rubber material is improved. Heat generation is reduced, the rolling resistance of the tire can be reduced, oil consumption is reduced, the excellent cord thread drawing force is achieved, and the safety performance of tire running is improved. Tyres use a large amount of rubber materials and need a large amount of reinforcing agents. When the thermal cracking carbon black is used in the tire, popularization and application of the thermal cracking carbon black can be further promoted, cyclic utilization of the tire is promoted, the environment is improved, and carbon neutralization is achieved.

Description

Technical Field

[0001] The invention relates to the field of tires, and in particular to a cracked carbon black reinforced tire transition layer rubber material and a preparation method thereof. Background Art

[0002] At present, the carbon black generally used for tire reinforcement is mainly derived from petrochemical products, not renewable resources. The country advocates a sustainable development strategy, reduces the proportion of petrochemicals, increases the utilization rate of renewable resources, and achieves carbon neutrality. Waste tires have a very slow natural degradation rate, are difficult to degrade, have a low recycling rate, and have a great impact on the environment. Only deep processing can effectively treat them. Thermal cracking is the most effective way to recycle tires. As one of the cracking products, thermal cracking carbon black accounts for 30-35% of the total cracking products. There is a large gap between its composition and reinforcement effect and commercial carbon black. It is necessary to find a reasonable treatment. If it can be used reasonably, it will not only reduce resource waste, but also reduce tire pollution to the environment. It is imperative to develop the use of thermal cracking carbon black. Tires are the largest category of rubber products and the product that uses the most reinforcement materials. Using thermal cracking carbon black in tires can greatly increase the use of thermal cracking carbon black. Thermal cracking carbon black is mainly composed of carbon black, but its ash content is high. It is mainly composed of white carbon black and zinc oxide, which leads to its reinforcement effect not reaching the effect of commercial carbon black. Thermal carbon black is currently mainly used in small products such as seals to reduce costs, and its usage is low.

[0003] The transition layer is a layer of rubber between the tire body and the airtight layer. Its function is to improve the adhesion between the airtight layer and the tire body cord layer to prevent the tire from delaminating during use. This requires the transition layer rubber to have high viscosity and good adhesion between the rubber and the steel wire.

[0004] Patent application CN201410129428.6 discloses a tire transition layer rubber material, which is prepared by mixing the following raw materials in parts by weight: natural rubber: 100 parts, carbon black: 40 to 60 parts, reinforcing tackifier RF-1: 10 to 15 parts, zinc oxide: 6 to 9 parts, antioxidant 4020: 1.0 to 2.0 parts, adhesive antioxidant BW-60: 1.5 to 2.5 parts, resorcinol formaldehyde resin: 1.0 to 2.0 parts, tackifying resin: 2 to 4 parts, rubber tackifier SKM-1: 2.0 to 3.0 parts, adhesive RA-65: 4.0 to 6.0 parts, sulfur: 4.0 to 6.0 parts, and accelerator DZ: 1.0 to 2.0 parts. The transition layer rubber improves the self-adhesiveness and mutual adhesiveness of the rubber to a certain extent, and increases the bonding performance between the rubber and the steel wire, but the rolling resistance is large, the cord extraction force is low, and the product is rough. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects of the above-mentioned prior art and provide a cracked carbon black reinforced tire transition layer rubber and its preparation method, which can reduce heat generation, reduce the rolling resistance of the tire, improve the cord extraction force, and improve the safety performance of tire driving.

[0006] The object of the present invention can be achieved by the following technical scheme: A pyrolysis carbon black reinforced tire transition layer rubber material, comprising the following components in parts by weight:

[0007] Head glue: 93.5-97.5;

[0008] Sulfur: 2-6;

[0009] Accelerator: 0.3-0.8;

[0010] Anti-scorching agent: 0.1-0.5.

[0011] Furthermore, the head section glue comprises the following components in parts by weight:

[0012] Natural rubber: 40-60;

[0013] Carbon black: 30-50;

[0014] Thermal black: 5-15;

[0015] Zinc oxide: 3-10;

[0016] Anti-aging agent: 2-6;

[0017] Cobalt boroacylate: 0.2-1.

[0018] Furthermore, the head section glue is prepared by the following method:

[0019] S01: natural rubber, carbon black, thermal cracking carbon black and antioxidant are added into an internal mixer for mixing at a pressure of 0.55-0.65 MPa and a rotation speed of 40-50 rpm for 25-35 seconds;

[0020] S02 Add zinc oxide and cobalt borate into an internal mixer for mixing at a pressure of 0.55-0.65 MPa and a rotation speed of 35-45 rpm for 20-30 seconds;

[0021] After S03 lifts the bolt, press the bolt after a 5-second pause, with a pressure of 0.55-0.65MPa, a rotation speed of 30-40rpm, and mix until the temperature reaches 150-170℃ for glue discharge;

[0022] After S04 passes through a tablet press, it is cooled and collected to obtain the first-stage glue.

[0023] Furthermore, the natural rubber is dried in a drying room at a temperature of 50-70° C. before use to eliminate internal crystallization and improve processing performance.

[0024] Furthermore, the thermal cracking carbon black is commercially available thermal cracking carbon black, and EN660 from Anhui Province Clintel Renewable Resources Technology Co., Ltd. is selected. Domestic thermal cracking carbon black is preferred to provide part of zinc oxide and white carbon black for the rubber compound to improve the adhesion between the rubber compound and the cord.

[0025] Furthermore, the natural rubber is TSR20 rubber, thereby improving the tensile properties of the rubber; the carbon black is N326 low-structure carbon black, thereby improving the tensile properties of the rubber, while retaining the fluidity of the rubber, ensuring that the rubber flows in the cord, enhancing the adhesion and bonding between the rubber and the cord, thereby improving the cord fabric extraction force.

[0026] Furthermore, the antioxidant is an anti-thermal oxidative aging type antioxidant, which increases the aging performance of the rubber material, including antioxidant 4020.

[0027] Select insoluble sulfur to prevent frosting of vulcanized rubber and improve the processing performance of the rubber.

[0028] Furthermore, the accelerator is a sulfonamide accelerator, including accelerator NS, which has a long scorch time and high operating safety, and its vulcanized rubber has good physical and dynamic properties, which is beneficial to improving the bonding performance between rubber and brass-plated steel cord.

[0029] Furthermore, the anti-scorching agent includes anti-scorching agent CTP.

[0030] Cobalt borate is selected from high-quality domestic suppliers, which increases the bonding strength between the cord and the rubber, thereby improving the withdrawal force of the cord.

[0031] The present invention also provides a method for preparing a pyrolysis carbon black reinforced tire transition layer rubber material, comprising the following steps:

[0032] S11: Add the head rubber, sulfur, accelerator and scorch retarder into the internal mixer, with a pressure of 0.45-0.55MPa and a speed of 20-30rpm, and mix for 20-30 seconds;

[0033] S12 After lifting the bolt, press the bolt after a 5-second pause, with a pressure of 0.45-0.55MPa, a rotation speed of 20-30rpm, and mixing for 20-30 seconds;

[0034] After S13 lifts the bolt, press the bolt after a 5-second pause, with a pressure of 0.45-0.55MPa and a rotation speed of 20-30rpm, and mix until the temperature reaches 95-105℃ for glue discharge;

[0035] After S14 is discharged from the mixing mill, it is cooled and collected to obtain the transition layer rubber material.

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

[0037] 1. The present invention reduces heat generation, can reduce the rolling resistance of tires, save fuel consumption, has excellent cord extraction force, and improves the safety performance of tire driving. Tires use a large amount of rubber and require a large amount of reinforcing agents. The use of thermal cracking carbon black in tires can further promote the promotion and use of thermal cracking carbon black, promote the recycling of tires, improve the environment, and achieve carbon neutrality.

[0038] 2. The present invention adopts a specially formulated head rubber, and utilizes thermal cracking carbon black to partially replace normal carbon black in the tire transition layer formula, which can provide part of zinc oxide and white carbon black for the formula, and is combined with ordinary commercially available carbon black, cobalt borate, etc., wherein the carbon element can combine with the rubber to play a reinforcing role and provide material strength, and non-metallic elements such as oxygen, nitrogen, silicon, sulfur, etc., metal elements such as zinc, aluminum, etc., and filler silica used to replace carbon black, etc., can play a role in vulcanization, activate the performance of the accelerator, improve the vulcanization efficiency, and improve the bonding performance, thereby increasing the cord withdrawal force without reducing the tensile performance of the tire transition layer rubber, and improving its heat generation performance, thereby enhancing the safety performance of the tire driving.

[0039] 3. The head rubber prepared by a special method in the present invention can work synergistically with sulfur, accelerators and anti-scorching agents to improve the surface viscosity of the rubber and the cord extraction force of the rubber, and reduce the heat generation performance of the rubber. Reducing heat generation can reduce the rolling resistance of the tire, save fuel consumption, and the excellent cord extraction force can improve the safety performance of the tire. Tires use a large amount of rubber and require a large amount of reinforcing agents. The use of thermal cracking carbon black in tires can further promote the promotion and use of thermal cracking carbon black, promote the recycling of tires, improve the environment, achieve carbon neutrality, and reduce the use of reinforcing agents.

[0040] 4. The pyrolysis carbon black used in the present invention is a product of deep processing of waste tires. The pyrolysis carbon black is used in the tire transition layer rubber material, which is equivalent to processing scrap tires and is environmentally friendly. DETAILED DESCRIPTION

[0041] The present invention is described in detail below with reference to specific embodiments.

[0042] The various raw materials used in the present invention are all commercially available products.

[0043] Example 1

[0044] A cracked carbon black reinforced tire transition layer rubber material is prepared by the following method:

[0045] (I) Preparation of head glue:

[0046] 11) Prepare the materials according to the following components and contents:

[0047] Natural rubber: 50kg

[0048] Carbon black: 28 kg. In this embodiment, N660 carbon black from Jiangxi Black Cat Carbon Black Co., Ltd. is used.

[0049] Thermal cracking carbon black: 8 kg In this embodiment, EN660 from Anhui Clintel Renewable Resources Technology Co., Ltd. is selected.

[0050] Zinc oxide: 5kg

[0051] Anti-aging agent: 5kg, in this embodiment, the antioxidant 4020 from Shandong Shangshun Chemical Co., Ltd. is selected

[0052] Cobalt borate: 0.4 kg. In this example, cobalt borate from Dalian Aibosi Chemical Co., Ltd. was selected.

[0053] 12) Bake the natural rubber at 60°C to eliminate internal crystallization and improve processing performance.

[0054] 13) natural rubber, carbon black, thermal cracking carbon black and antioxidant were added into an internal mixer and mixed at a pressure of 0.6 MPa and a rotation speed of 45 rpm for 30 seconds;

[0055] 14) Add zinc oxide and cobalt borate into an internal mixer and mix them at a pressure of 0.6 MPa and a speed of 40 rpm for 25 seconds;

[0056] 15) After lifting the plug, press the plug after a 5-second pause, with a pressure of 0.6 MPa and a rotation speed of 30 rpm, and mix until the temperature reaches 160°C for degumming.

[0057] 16) After passing through a tablet press, the mixture is cooled and collected to obtain the first-stage glue.

[0058] (II) Preparation of transition layer rubber:

[0059] 21) Prepare the materials according to the following components and contents:

[0060] Head rubber: 96.4kg

[0061] Sulfur: 3kg

[0062] Accelerator: 0.4kg

[0063] Anti-scorching agent: 0.2kg

[0064] 22) Add the first section rubber, sulfur, accelerator and scorch retarder into the internal mixer, with a pressure of 0.5 MPa and a speed of 25 rpm, and mix for 25 seconds;

[0065] 23) After lifting the plug, pause for 5 seconds and then press the plug, with a pressure of 0.5 MPa, a rotation speed of 25 rpm, and mix for 25 seconds.

[0066] 24) After lifting the plug, pause for 5 seconds and then press the plug, with a pressure of 0.5 MPa and a rotation speed of 20 rpm, and mix until the temperature reaches 100°C for degumming.

[0067] 25) After being discharged from the mixing mill, the flakes are cooled and collected to obtain the vulcanized rubber.

[0068] Example 2

[0069] A cracked carbon black reinforced tire transition layer rubber material is prepared by the following method:

[0070] (I) Preparation of head glue:

[0071] 11) Prepare the materials according to the following components and contents:

[0072] Natural rubber: 40kg

[0073] Carbon black: 33.3 kg. In this embodiment, N660 carbon black from Jiangxi Black Cat Carbon Black Co., Ltd. is used.

[0074] Thermal cracking carbon black: 15kg In this embodiment, EN660 from Anhui Clintel Renewable Resources Technology Co., Ltd. is selected

[0075] Zinc oxide: 3kg

[0076] Anti-aging agent: 2kg, in this embodiment, the antioxidant 4020 from Shandong Shangshun Chemical Co., Ltd. is selected

[0077] Cobalt borate: 0.2 kg. In this example, cobalt borate from Dalian Aibosi Chemical Co., Ltd. was used.

[0078] 12) Bake the natural rubber at 70°C to eliminate internal crystallization and improve processing performance.

[0079] 13) adding natural rubber, carbon black, thermal cracking carbon black and antioxidant into an internal mixer and mixing them at a pressure of 0.55 MPa and a rotation speed of 40 rpm for 25 seconds;

[0080] 14) Add zinc oxide and cobalt borate into an internal mixer and mix them at a pressure of 0.55 MPa and a rotation speed of 35 rpm for 20 seconds;

[0081] 15) After lifting the plug, pause for 5 seconds and then press the plug, with a pressure of 0.55 MPa and a rotation speed of 30 rpm, and mix until the temperature reaches 150°C for degumming.

[0082] 16) After passing through a tablet press, the mixture is cooled and collected to obtain the first-stage glue.

[0083] (II) Preparation of transition layer rubber:

[0084] 21) Prepare the materials according to the following components and contents:

[0085] Head rubber: 93.5kg

[0086] Sulfur: 5.2kg

[0087] Accelerator: 0.8kg

[0088] Anti-scorching agent: 0.5kg

[0089] 22) Add the first section rubber, sulfur, accelerator and scorch retarder into the internal mixer, with a pressure of 0.45 MPa and a speed of 20 rpm, and mix for 20 seconds;

[0090] 23) After lifting the plug, rest for 5 seconds and then press the plug, with a pressure of 0.45 MPa, a rotation speed of 20 rpm, and mix for 20 seconds.

[0091] 24) After lifting the plug, press the plug after a 5-second pause, with a pressure of 0.45 MPa and a rotation speed of 20 rpm, and mix to 95°C for degumming.

[0092] 25) After being discharged from the mixing mill, the flakes are cooled and collected to obtain the vulcanized rubber.

[0093] Example 3

[0094] A cracked carbon black reinforced tire transition layer rubber material is prepared by the following method:

[0095] (I) Preparation of head glue:

[0096] 11) Prepare the materials according to the following components and contents:

[0097] Natural rubber: 55.3kg

[0098] Carbon black: 30 kg. In this embodiment, N660 carbon black from Jiangxi Black Cat Carbon Black Co., Ltd. is used.

[0099] Thermal cracking carbon black: 5kg In this embodiment, Anhui Province Clintel Renewable Resources Technology Co., Ltd. EN660

[0100] Zinc oxide: 3kg

[0101] Anti-aging agent: 4 kg, in this embodiment, the antioxidant 4020 from Shandong Shangshun Chemical Co., Ltd. is selected

[0102] Cobalt borate: 0.2 kg. In this example, cobalt borate from Dalian Aibosi Chemical Co., Ltd. was selected.

[0103] 12) Bake the natural rubber at 50°C to eliminate internal crystallization and improve processing performance.

[0104] 13) adding natural rubber, carbon black, thermal cracking carbon black and antioxidant into an internal mixer and mixing them at a pressure of 0.65 MPa and a rotation speed of 50 rpm for 35 seconds;

[0105] 14) Add zinc oxide and cobalt borate to an internal mixer and mix them at a pressure of 0.65 MPa and a speed of 45 rpm for 30 seconds;

[0106] 15) After lifting the plug, press the plug after a 5-second pause, with a pressure of 0.65 MPa and a rotation speed of 40 rpm, and mix until the temperature reaches 170°C for degumming.

[0107] 16) After passing through a tablet press, the mixture is cooled and collected to obtain the first-stage glue.

[0108] (II) Preparation of transition layer rubber:

[0109] 21) Prepare the materials according to the following components and contents:

[0110] Head rubber: 97.5kg

[0111] Sulfur: 2kg

[0112] Accelerator: 0.3kg

[0113] Anti-scorching agent: 0.1kg

[0114] 22) Add the first section rubber, sulfur, accelerator and scorch retarder into the internal mixer, with a pressure of 0.55 MPa and a speed of 30 rpm, and mix for 30 seconds;

[0115] 23) After lifting the plug, rest for 5 seconds and then press the plug, with a pressure of 0.55 MPa, a rotation speed of 30 rpm, and mix for 30 seconds.

[0116] 24) After lifting the plug, press the plug after a 5-second pause, with a pressure of 0.55 MPa and a rotation speed of 30 rpm, and mix until the temperature reaches 105°C for degumming.

[0117] 25) After being discharged from the mixing mill, the flakes are cooled and collected to obtain the vulcanized rubber.

[0118] Comparative Example

[0119] Thermal cracking carbon black is all carbon black, that is, the amount of carbon black is 36 kg, and the rest is the same as Example 1.

[0120] The transition layer rubber materials obtained in Examples 1-3 and the comparative example were made into tires according to conventional methods, and the performance tests were carried out as follows:

[0121] Testing method: In Tables 1 to 3 below, the performance testing methods are as follows:

[0122] The tensile strength is tested according to GB / T 528;

[0123] The elongation at break is tested according to GB / T 528;

[0124] Tb*Eb is tested according to GB / T 528;

[0125] The cord withdrawal force is tested according to GB / T 16586; the formulas of the above-mentioned embodiments and comparative examples are as follows:

[0126] raw material Recipe Range Example 1 Example 2 Example 3 Comparative Example Head glue 93.5-97.5 96.4 93.5 97.5 96.4 Natural rubber 40-60； 50 40 55.3 50 Carbon Black 30-50； 28 33.3 30 36 Thermal Carbon Black 5-15； 8 15 5 0 Zinc Oxide 3-10； 5 3 3 5 Antioxidant 2-6； 5 2 4 5 Cobalt boroacylate 0.2-1 0.4 0.2 0.2 0.4 sulfur: 2.0-6.0 3 5.2 2 3 Accelerator 0.3-0.8 0.4 0.8 0.3 0.4 Anti-scorch agent 0.1-0.5 0.2 0.5 0.2 0.2

[0127] Table 1

[0128]

[0129] Main technical indicators: Table 2

[0130]

[0131]

[0132] Main technical indicators: Table 3

[0133]

[0134] From Tables 1 to 3, it can be seen that adding thermal cracking carbon black to the tire transition layer rubber can reduce the rubber's tensile strength, enhance the elongation, Tb*Eb, and cord withdrawal force, reduce the rubber's compression heat generation and hysteresis loss, and improve the rubber's rolling performance and fuel saving.

[0135] The above examples are only reference embodiments of the present invention. The scope defined by the claims of the present invention is not limited by the above specific implementation details. It should be understood that any modifications, concentration changes, similar component replacements and modifications made to the present invention by those skilled in the art in accordance with the design principles of the present invention should be within the protection scope of the present invention.

Claims

1. A pyrolysis carbon black reinforced tire transition layer rubber material, characterized in that: The composition comprises the following components in parts by weight: Head glue: 93.5-97.5; Sulfur: 2-6; Accelerator: 0.3-0.8; Anti-scorching agent: 0.1-0.

5.

2. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 1, characterized in that: The head section glue comprises the following components in parts by weight: Natural rubber: 40-60; Carbon black: 30-50; Thermal black: 5-15; Zinc oxide: 3-10; Anti-aging agent: 2-6; Cobalt borate: 0.2-1.

3. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 2, characterized in that: The head section glue is prepared by the following method: S01: natural rubber, carbon black, thermal cracking carbon black and antioxidant are added into an internal mixer for mixing at a pressure of 0.55-0.65 MPa and a rotation speed of 40-50 rpm for 25-35 seconds; S02 Add zinc oxide and cobalt borate into an internal mixer for mixing at a pressure of 0.55-0.65 MPa and a rotation speed of 35-45 rpm for 20-30 seconds; After S03 lifts the bolt, press the bolt after a 5-second pause, with a pressure of 0.55-0.65MPa, a rotation speed of 30-40rpm, and mix until the temperature reaches 150-170℃ for glue discharge; After S04 passes through a tablet press, it is cooled and collected to obtain the first-stage glue.

4. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 3, characterized in that: The natural rubber is baked at 50-70°C before use to eliminate internal crystallization and improve processing performance.

5. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 2, characterized in that: The thermal cracking carbon black is commercially available EN660 thermal cracking carbon black.

6. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 2, characterized in that: The natural rubber is TSR20 rubber; the carbon black is low-structure carbon black N326.

7. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 2, characterized in that: The antioxidant is a heat-oxidative aging-resistant antioxidant, including antioxidant 4020.

8. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 1, characterized in that: The accelerator is a sulfonamide accelerator, including accelerator NS.

9. The pyrolysis carbon black reinforced tire transition layer rubber material according to claim 1, characterized in that: The anti-scorching agent includes anti-scorching agent CTP.

10. A method for preparing a pyrolysis carbon black reinforced tire transition layer rubber material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S11: Add the head rubber, sulfur, accelerator and scorch retarder into the internal mixer, with a pressure of 0.45-0.55MPa and a speed of 20-30rpm, and mix for 20-30 seconds; S12 After lifting the bolt, press the bolt after a 5-second pause, with a pressure of 0.45-0.55MPa, a rotation speed of 20-30rpm, and mixing for 20-30 seconds; After S13 lifts the bolt, press the bolt after a 5-second pause, with a pressure of 0.45-0.55MPa and a rotation speed of 20-30rpm, and mix until the temperature reaches 95-105℃ for glue discharge; After S14 is discharged from the mixing mill, it is cooled and collected to obtain the transition layer rubber material.

Images