CN112778580A - All-steel tire nylon cord fabric rubber material and preparation method thereof - Google Patents
All-steel tire nylon cord fabric rubber material and preparation method thereof Download PDFInfo
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- CN112778580A CN112778580A CN202011578510.9A CN202011578510A CN112778580A CN 112778580 A CN112778580 A CN 112778580A CN 202011578510 A CN202011578510 A CN 202011578510A CN 112778580 A CN112778580 A CN 112778580A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to the technical field of tire processing, in particular to a nylon cord rubber material for an all-steel tire and a preparation method thereof. The all-steel tire nylon cord fabric sizing material is mainly prepared from rubber, a compounding agent A and a compounding agent B; the rubber comprises 80-100 parts by mass of natural rubber; the compounding agent A comprises the following raw materials in parts by mass: 50-60 parts of carbon black, 5-7 parts of aromatic oil, 8-16 parts of phenolic reinforcing resin and 6-12 parts of high styrene resin; the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203-4 parts and hexamethylenetetramine 0.8-1.6 parts. The all-steel tire nylon cord fabric rubber material has excellent performance in all aspects, particularly has more remarkable performance in reinforcing and processing performances, and the Shore hardness of the produced rubber material can reach more than 80 at normal temperature.
Description
Technical Field
The invention relates to the technical field of tire processing, in particular to a nylon cord rubber material for an all-steel tire and a preparation method thereof.
Background
The all-steel truck radial tire is the most widely used commercial tire at present, and has higher wear resistance, safety, comfort and stability than the diagonal tire. The tire is often used as an engineering machinery tire, a mining tire, a long-distance truck tire and a short-distance truck tire.
The rubber material of each part of the all-steel truck radial tire has higher requirements on heat generation and definite elongation, so that the formula has high natural rubber content and less processing assistant amount of oil and the like. The all-steel truck radial tire still needs to use nylon cord at certain specific parts. However, even if the rubber material is nylon cord skim coating, the performance of the rubber material of all-steel truck radial tires also requires comprehensive properties such as higher hardness, and if the hardness is improved by adding reinforcing means such as carbon black according to the conventional method, the processing is greatly difficult. At present, the nylon cord fabric is calendered by adopting a frictioning process basically, the calendering speed is high, but the processing performance of mixed rubber is high, otherwise scorching damage is easy to occur, the appearance quality of the cord fabric is not good, the surface viscosity is not good, and the like. Not only causes the increase of the manufacturing cost, but also easily causes the early damage of the tire because the quality of the cord fabric is poor.
In view of the wide application of nylon cord in all-steel tires, it is still rare that the quality of the cord (old rubber, non-sticking and delaminating) is poor, and the early damage of the tire is caused.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nylon cord fabric rubber material for an all-steel tire, which has excellent performance in all aspects, particularly has more remarkable performance in reinforcement and processing performance, and the Shore hardness of the produced rubber material can reach more than 80 at normal temperature.
The second purpose of the invention is to provide a preparation method of the all-steel tire nylon cord fabric rubber material, which is simple and feasible, reduces 2 stages compared with the mixing stage number of the same hardness formula, reduces the calendering waste material and improves the calendering cord fabric quality.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
an all-steel tire nylon cord fabric sizing material is mainly prepared from rubber, a compounding agent A and a compounding agent B;
the rubber comprises 80-100 parts by mass of natural rubber;
the compounding agent A comprises the following raw materials in parts by mass: 50-60 parts of carbon black, 5-7 parts of aromatic oil, 8-16 parts of phenolic reinforcing resin and 6-12 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203-4 parts and hexamethylenetetramine 0.8-1.6 parts.
Preferably, the natural rubber accounts for 90-100 parts by mass;
the compounding agent A comprises the following raw materials in parts by mass: 52-56 parts of carbon black, 5.5-6.2 parts of aromatic oil, 8-12 parts of phenolic reinforcing resin and 6-10 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203.5-4 parts and hexamethylenetetramine 0.8-1.2 parts;
preferably, the natural rubber accounts for 100 parts by mass;
the compounding agent A comprises the following raw materials in parts by mass: 55 parts of carbon black, 6 parts of aromatic oil, 14 parts of phenolic reinforcing resin and 10 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-204 parts and hexamethylenetetramine 1.4 parts.
Preferably, the rubber further comprises 1-20 parts by mass of styrene butadiene rubber;
preferably, the styrene butadiene rubber accounts for 1-10 parts;
preferably, the styrene-butadiene rubber is SBR 1500E.
Preferably, the compounding agent A further comprises 4-8 parts of an activating agent in parts by mass;
preferably, the activator comprises zinc oxide and/or stearic acid;
preferably, the compounding agent A further comprises 2-5 parts of an anti-aging agent in parts by mass;
preferably, the antioxidant comprises antioxidant RD.
Preferably, the compounding agent B further comprises 0.1-1 part by mass of an accelerator;
preferably, the accelerator comprises an accelerator TBBS;
preferably, the compounding agent B further comprises 0.2-0.5 part of a scorch retarder in parts by mass;
preferably, the scorch retarder comprises the scorch retarder CTP.
Preferably, the phenolic reinforcing resin comprises polymerized oil NC-360HP and/or tall oil modified phenolic reinforcing resin with reinforcing effect obtained by polymerizing and modifying cashew nut oil as a raw material;
preferably, the high styrene resin is a copolymer of styrene and butadiene, wherein the styrene content is 70 wt% to 85 wt%;
preferably, the carbon black comprises N375 carbon black;
preferably, the natural rubber is 20# standard rubber.
The preparation method of the nylon cord rubber material for the all-steel tire comprises the following steps:
and (3) mixing the plasticated rubber with the mixture of the accessory ingredient A, and then mixing with the accessory ingredient B for mixing.
Preferably, the mastication of the rubber comprises the steps of:
adding rubber into an internal mixer, pressing for 35-45 s, extracting the plug for 25-35 s, and pressing the plug to 165-170 ℃ for discharging;
preferably, the rotating speed of the internal mixer is 25-35 rpm;
preferably, the material is discharged and then placed for 4-8 h.
Preferably, the mixing of the mixture of the masticated rubber and the compounding agent a includes:
mixing the solid material of the compounding agent A with plasticated rubber, pressing the mixture for 25-30 seconds, adding the liquid material of the compounding agent A after extracting the mixture, keeping the extraction for 4-6 seconds after pressing the mixture for 25-35 seconds, and pressing the mixture to 165-170 ℃ for discharging;
preferably, in the process of mixing the mixture of the plasticated rubber and the compounding agent A, the rotating speed of an internal mixer is 50-60 rpm;
preferably, the material is discharged and then placed for 8-24 h.
Preferably, the mixing and mixing with the compounding ingredient B further comprises:
the plug is pressed for 15-25 s, the plug is lifted for 4-6 s, the plug is pressed for 25-35 s, the plug is lifted for 4-6 s, and the plug is pressed to 95-105 ℃ and then discharged;
preferably, the rotating speed of the internal mixer is 18-25 rpm in the process of mixing with the compounding agent B for mixing.
Compared with the prior art, the invention has the beneficial effects that:
(1) the all-steel tire nylon cord fabric rubber material has excellent performance in all aspects, particularly has more remarkable performance in reinforcing and processing performances, and the Shore hardness of the produced rubber material can reach more than 80 at normal temperature.
(2) The preparation method of the all-steel tire nylon cord fabric rubber material is simple and easy to implement, the number of mixing sections is reduced by 2 sections compared with the same hardness formula, the calendering waste is reduced, and the calendering cord fabric quality is improved. The processing difficulty is greatly reduced while the physical properties such as high hardness and the like are considered, the quality of the tire is improved, and the production energy consumption and the cost are reduced.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
According to one aspect of the invention, the invention relates to an all-steel tire nylon cord rubber material which is mainly prepared from rubber, a compounding agent A and a compounding agent B;
the rubber comprises 80-100 parts by mass of natural rubber;
the compounding agent A comprises the following raw materials in parts by mass: 50-60 parts of carbon black, 5-7 parts of aromatic oil, 8-16 parts of phenolic reinforcing resin and 6-12 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203-4 parts and hexamethylenetetramine 0.8-1.6 parts.
In one embodiment, 80 to 100 parts of the natural rubber may be selected from 80 parts, 81 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts and 100 parts.
In one embodiment, the carbon black is 50 to 60 parts, and may be selected from 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts and 60 parts.
In one embodiment, the aromatic oil is 5 to 7 parts, and may be selected from 5 parts, 5.5 parts, 6 parts, 6.5 parts and 7 parts.
In one embodiment, the phenolic reinforcing resin is 8-16 parts, and optionally 8, 9, 10, 11, 12, 13, 14, 15 or 16 parts.
In one embodiment, the high styrene resin is 6 to 12 parts, and optionally 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts.
In one embodiment, the insoluble sulfur OT-203-4 parts may be 3 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, or 4 parts.
In one embodiment, the hexamethylenetetramine is 0.8 to 1.6 parts, and optionally 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts or 1.6 parts.
Preferably, the natural rubber accounts for 90-100 parts by mass;
the compounding agent A comprises the following raw materials in parts by mass: 52-56 parts of carbon black, 5.5-6.2 parts of aromatic oil, 8-12 parts of phenolic reinforcing resin and 6-10 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203.5-4 parts and hexamethylenetetramine 0.8-1.2 parts.
Preferably, the natural rubber accounts for 100 parts by mass;
the compounding agent A comprises the following raw materials in parts by mass: 55 parts of carbon black, 6 parts of aromatic oil, 14 parts of phenolic reinforcing resin and 10 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-204 parts and hexamethylenetetramine 1.4 parts.
Preferably, the rubber further comprises 1-20 parts by mass of styrene butadiene rubber.
Preferably, the styrene butadiene rubber accounts for 1-10 parts;
preferably, the styrene-butadiene rubber is SBR 1500E.
Preferably, the compounding agent A further comprises 4-8 parts of an activating agent in parts by mass.
In one embodiment, the compounding agent a further comprises 4-8 parts of an activating agent, and further 4 parts, 5 parts, 6 parts, 7 parts or 8 parts can be selected.
Preferably, the activator comprises zinc oxide and/or stearic acid.
Preferably, the activator comprises 2-4 parts of zinc oxide and 2-4 parts of stearic acid.
Preferably, the compounding agent A further comprises 2-5 parts of an anti-aging agent in parts by mass.
In one embodiment, the compounding agent a further comprises 2 to 5 parts of an anti-aging agent, and may be selected from 2 parts, 3 parts, 4 parts or 5 parts.
Preferably, the antioxidant comprises antioxidant RD.
The invention has excellent effect of preventing aging caused by heat and oxygen by adding a proper amount of the antioxidant RD.
Preferably, the compounding agent B further comprises 0.1-1 part by mass of an accelerator.
In one embodiment, the accelerator is 0.1 to 1 part, and optionally 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part.
Preferably, the accelerator comprises an accelerator TBBS.
Preferably, the compounding agent B further comprises 0.2-0.5 part of a scorch retarder in parts by mass.
In one embodiment, the scorch retarder is 0.2-0.5 parts, and optionally 0.2 parts, 0.3 parts, 0.4 parts, or 0.5 parts.
Preferably, the scorch retarder comprises the scorch retarder CTP.
Preferably, the phenolic reinforcing resin comprises polymerized oil NC-360HP and/or tall oil modified phenolic reinforcing resin with reinforcing effect obtained by polymerizing and modifying cashew nut oil as a raw material.
Preferably, the tall oil-modified phenolic reinforcing resin is tall oil-modified phenolic reinforcing resin SP 6701.
Preferably, the high styrene resin is a copolymer of styrene and butadiene, wherein the styrene content is 70 wt% to 85 wt%.
According to the invention, a proper amount of reinforcing material is adopted to partially replace carbon black to reduce the processing problem caused by carbon black reinforcement, so that not only can the mechanical property better than that of high-consumption carbon black be obtained, but also the processing temperature can be reduced due to the functions of the resin as a softener and a plasticizer, and the safety and quality uniformity of rubber material mixing are ensured. Among them, the high styrene resin has a remarkable plastic property, good flowability in a hot state, and a great relationship between the resin properties and the styrene content, and the strength, rigidity and hardness of the high styrene resin are improved with the increase of the styrene content, but the high styrene resin contains double bonds and can be co-crosslinked with rubber. The phenolic resin is thermal reaction type thermoplastic phenolic resin, generates a three-dimensional structure through cross-linking reaction with methylene, and endows vulcanized rubber with reinforcing and hardening performances, and the liquid cashew nut oil modified phenolic resin applied in the invention is polymerized oil obtained by polymerizing and modifying cashew nut oil as a raw material, has the reinforcing characteristic similar to that of the phenolic resin, but has better fluidity. When the resin is applied to the formula, the performance requirement of the rubber material can be ensured, the energy reduction of the rubber material mixing of the formula is facilitated, the Mooney reduction of the mixed rubber material is facilitated, the scorched and broken material generation during the nylon cord fabric calendering is facilitated to be reduced, the appearance and the viscosity quality of the cord fabric can be improved, and the integral quality of the tire is facilitated to be improved.
Preferably, the carbon black comprises N375 carbon black.
According to the nylon cord fabric skim coating rubber material, the use amount of the high natural rubber, the use amount of the low processing aid, the appropriate use amount and variety of the carbon black are adopted, a matched rubber material system of the reinforcing resin is combined, the components are matched with each other, particularly the selection of the variety and the use amount of the reinforcing resin is carried out, so that the performance of each aspect of the produced rubber material is excellent, the reinforcing and processing performances are more remarkable, the Shore hardness of the produced rubber material can reach more than 80 at normal temperature, after the traditional primary rubber and primary final mixing are adopted, the Mooney viscosity ML (1+4) can reach about 60 at 100 ℃, 2 sections are reduced compared with the mixing section number of the same hardness formula, the rolling waste is reduced, and the quality of the rolled cord fabric is improved.
Preferably, the natural rubber is 20# standard rubber.
According to another aspect of the invention, the invention relates to a preparation method of the nylon cord fabric sizing material for the all-steel tire, which comprises the following steps:
and (3) mixing the plasticated rubber with the mixture of the accessory ingredient A, and then mixing with the accessory ingredient B for mixing.
The preparation method is simple and feasible.
Preferably, the mastication of the rubber comprises the steps of:
adding rubber into an internal mixer, pressing for 35-45 s, lifting for 25-35 s, pressing for 165-170 ℃ and discharging.
In one embodiment, the pressure bolt is used for 35-45 s in the plastication of the rubber, and can be selected from 37s, 40s and 43 s. The lifting bolt is kept for 25-35 s, and can be selected from 25s, 26s, 27s, 28s, 29s, 30s, 31s, 32s, 33s, 34s or 35 s. Pressing the mixture to 165-170 ℃ for discharging, and selecting 165 ℃, 166 ℃, 167 ℃, 168 ℃, 169 ℃ or 170 ℃.
Preferably, the rotating speed of the internal mixer is 25-35 rpm.
In one embodiment, the rotation speed of the internal mixer is 25-35 rpm, and 25s, 26s, 27s, 28s, 29s, 30s, 31s, 32s, 33s, 34s or 35s can be selected.
Preferably, the material is discharged and then placed for 4-8 h. In one embodiment, the discharge is followed by 4h, 5h, 6h, 7h or 8 h.
Preferably, the mixing of the mixture of the masticated rubber and the compounding agent a includes:
mixing the solid material of the compounding agent A with plasticated rubber, pressing and bolting for 25-30 s, adding the liquid material of the compounding agent A after bolting, keeping the bolting for 4-6 s after 25-35 s, and pressing and bolting to 165-170 ℃ for discharging.
In one embodiment, the solid material of the compounding agent A is mixed with the plasticated rubber, and the mixture is pressed for 25-30 s, and 25s, 26s, 27s, 28s, 29s or 30s can be selected. And adding the liquid material of the compounding agent A after the bolt is lifted, and pressing the bolt for 25-35 s, wherein 25s, 26s, 27s, 28s, 29s or 30s can be selected. The lifting bolt is kept for 4-6 s, and 4s, 5s or 6s can be selected. Pressing the mixture to 165-170 ℃ for discharging, and selecting 165 ℃, 166 ℃, 167 ℃, 168 ℃, 169 ℃ or 170 ℃.
Preferably, the rotation speed of an internal mixer is 50-60 rpm in the process of mixing the mixture of the plasticated rubber and the ingredient A.
In one embodiment, the rotation speed of the internal mixer is 50-60 rpm, and 50rpm, 51rpm, 52rpm, 53rpm, 54rpm, 55rpm, 56rpm, 57rpm, 58rpm, 59rpm or 60rpm can be selected.
Preferably, the material is discharged and then placed for 8-24 h.
In one embodiment, the material is discharged and then placed for 8-24 h, and 8h, 10h, 12h, 15h, 18h, 20h, 22h or 24h can be selected.
Preferably, the mixing and mixing with the compounding ingredient B further comprises:
and (3) after 15-25 s of bolt pressing, keeping the bolt lifting for 4-6 s, then after 25-35 s of bolt pressing, keeping the bolt lifting for 4-6 s, and then pressing the bolt to 95-105 ℃ for discharging.
In one embodiment, the press plug 15-25 s can be selected from 15s, 16s, 17s, 18s, 19s, 20s, 21s, 22s, 23s, 24s or 25 s. The lifting bolt is kept for 4-6 s, and 4.5s, 5s, 5.5s or 6s can be selected. The plug is pressed for 25-35 s, and can be selected from 25s, 28s, 30s, 32s or 35 s.
Preferably, the rotating speed of the internal mixer is 18-25 rpm in the process of mixing with the compounding agent B for mixing.
In one embodiment, the rotation speed of the internal mixer is 18-25 rpm, and 18rpm, 19rpm, 20rpm, 21rpm, 22rpm, 23rpm, 24rpm or 25rpm can be selected.
In one embodiment, the preparation method of the nylon cord fabric rubber material for the all-steel tire comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 25-35 rpm, adding natural rubber and butadiene rubber into the internal mixer, carrying out bolt extraction for 25-35 s after the bolt is pressed for 35-45 s, then pressing the bolt to 160-165 ℃ and discharging; standing for 4-8 h, and then mixing the master batch;
(b) mixing master batch: setting the rotating speed of an internal mixer to be 50-60 rpm, adding all solid materials except sulfur, an accelerator, hexamethylenetetramine and an anti-scorching agent into the internal mixer, pressing the mixture for 25-30 s, then extracting the mixture, adding liquid materials (such as aromatic oil and liquid cashew nut oil modified phenolic reinforcing resin) into the mixture, pressing the mixture for 25-35 s, keeping the extraction for 4-6 s, pressing the mixture to 165-170 ℃, and then discharging; standing for 8-24 h, and then mixing the mixture with final rubber;
(b) final mixing and milling: setting the rotating speed of an internal mixer to be 18-25 rpm, adding sulfur, an accelerator, hexamethylenetetramine and an anti-scorching agent into the internal mixer, carrying out bolt lifting for 4-6 s after 15-25 s of bolt pressing, carrying out bolt lifting for 4-6 s after 25-35 s of bolt pressing, then carrying out bolt pressing to 95-105 ℃, discharging to an open mill, and cooling to room temperature after a lower sheet.
The preparation method provided by the invention has the advantages of simple operation steps, close connection of the operation steps, mild operation conditions, greatly shortened operation time, saved operation cost and contribution to subsequent further expansion of application.
The present invention will be further explained with reference to specific examples and comparative examples.
Example 1
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
100.00 parts of natural rubber, 55.00 parts of N375 carbon black, 670114.00 parts of phenolic reinforced resin, 10.00 parts of high styrene resin, 6.00 parts of aromatic oil, 3.50 parts of zinc oxide, 3.00 parts of stearic acid, 1.00 part of anti-aging agent RD, 203.75 parts of sulfur OT, 1.40 parts of hexamethylenetetramine, 0.45 part of accelerator TBBS and 0.20 part of anti-scorching agent CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber into the internal mixer, carrying out bolt extraction for 30s after the bolt is pressed for 40s, and then carrying out discharge after the bolt is pressed to 165 ℃; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotation speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 30s, then adding a liquid material (aromatic oil and liquid cashew nut oil modified phenolic reinforcing resin) into the bolt, carrying out bolt pressing for 30s, keeping the bolt pressing for 5s, then carrying out bolt pressing to 165 ℃, and discharging; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotation speed of an internal mixer to be 20rpm, adding sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling to room temperature.
Example 2
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
100.00 parts of natural rubber, 55.00 parts of N375 carbon black, 14.00 parts of liquid cashew nut oil modified phenolic reinforcing resin (NC-360HP), 10.00 parts of high styrene resin, 6.00 parts of aromatic oil, 3.50 parts of zinc oxide, 3.00 parts of stearic acid, 1.00 parts of antioxidant RD, 1.40 parts of sulfur OT-203.75 parts of hexamethylenetetramine, 0.45 part of accelerator TBBS and 0.20 part of antiscorching agent CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber into the internal mixer, carrying out bolt extraction for 30s after the bolt is pressed for 40s, and then carrying out discharge after the bolt is pressed to 165 ℃; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotation speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 30s, then adding a liquid material (aromatic oil and liquid cashew nut oil modified phenolic reinforcing resin) into the bolt, carrying out bolt pressing for 30s, keeping the bolt pressing for 5s, then carrying out bolt pressing to 165 ℃, and discharging; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotation speed of an internal mixer to be 20rpm, adding sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling to room temperature.
Example 3
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
90.00 parts of natural rubber, 10.00 parts of styrene-butadiene rubber, 50.00 parts of N375 carbon black, 16.00 parts of liquid cashew oil modified phenolic reinforcing resin (NC-360HP), 12.00 parts of high styrene resin, 5.00 parts of aromatic oil, 3.50 parts of zinc oxide, 3.00 parts of stearic acid, 1.00 parts of anti-aging agent RD, sulfur OT-203.00 parts, 1.60 parts of hexamethylenetetramine, 0.45 part of accelerator TBBS and 0.20 part of anti-scorching agent CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber and styrene butadiene rubber into the internal mixer, pressing the bolt for 40s, extracting the bolt for 30s, pressing the bolt to 165 ℃, and discharging; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotation speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 30s, then adding a liquid material (aromatic oil and liquid cashew nut oil modified phenolic reinforcing resin) into the bolt, carrying out bolt pressing for 30s, keeping the bolt pressing for 5s, then carrying out bolt pressing to 165 ℃, and discharging; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotation speed of an internal mixer to be 20rpm, adding sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling to room temperature.
Example 4
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
80.00 parts of natural rubber, 20.00 parts of styrene-butadiene rubber, 60.00 parts of N375 carbon black, 67018.00 parts of phenolic reinforcing resin, 12.00 parts of high styrene resin, 5.00 parts of aromatic oil, 3.50 parts of zinc oxide, 3.00 parts of stearic acid, 1.00 parts of antioxidant RD, sulfur OT-204.00 parts, 0.80 part of hexamethylenetetramine, 0.45 part of accelerator TBBS and 0.20 part of scorch retarder CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber and styrene butadiene rubber into the internal mixer, pressing the bolt for 40s, extracting the bolt for 30s, pressing the bolt to 165 ℃, and discharging; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotation speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 30s, then adding a liquid material (aromatic oil and liquid cashew nut oil modified phenolic reinforcing resin) into the bolt, carrying out bolt pressing for 30s, keeping the bolt pressing for 5s, then carrying out bolt pressing to 165 ℃, and discharging; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotation speed of an internal mixer to be 20rpm, adding sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling to room temperature.
Example 5
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
80.00 parts of natural rubber, 20.00 parts of styrene-butadiene rubber, 60.00 parts of N375 carbon black, 670116.00 parts of phenolic reinforcing resin, 6.00 parts of high styrene resin, 7.00 parts of aromatic oil, 3.50 parts of zinc oxide, 3.00 parts of stearic acid, 1.00 parts of antioxidant RD, sulfur OT-204.00 parts, 1.60 parts of hexamethylenetetramine, 0.45 part of accelerator TBBS and 0.20 part of scorch retarder CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber and styrene butadiene rubber into the internal mixer, pressing the bolt for 40s, extracting the bolt for 30s, pressing the bolt to 165 ℃, and discharging; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotation speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 30s, then adding a liquid material (aromatic oil and liquid cashew nut oil modified phenolic reinforcing resin) into the bolt, carrying out bolt pressing for 30s, keeping the bolt pressing for 5s, then carrying out bolt pressing to 165 ℃, and discharging; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotation speed of an internal mixer to be 20rpm, adding sulfur, an accelerant, hexamethylene tetramine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling to room temperature.
Comparative example 1
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
100 parts of natural rubber, 5 parts of carbon black N37561 parts, 5 parts of zinc oxide, 1 part of stearic acid, 1 parts of anti-aging agent RD, 1.5 parts of anti-aging agent 6PPD, 802.5 parts of resorcinol-802.5 parts, 2 parts of phenolic tackifying resin, 205.5 parts of sulfur OT, 5 parts of hexamethoxymelamine, 1.3 parts of accelerator DZ and 2 parts of scorch retarder CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber into the internal mixer, carrying out bolt extraction for 30s after the bolt is pressed for 40s, and then carrying out discharge after the bolt is pressed to 165 ℃; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotating speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerator, hexamethoxymelamine and an anti-scorching agent into the internal mixer, carrying out bolt extraction for 30s after bolt pressing, adding a liquid material, carrying out bolt extraction for 5s after the bolt pressing for 30s, and then carrying out discharge after the bolt pressing is carried out to 165 ℃; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotating speed of an internal mixer to be 20rpm, adding sulfur, an accelerator, hexamethoxymelamine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling the lower piece to room temperature.
Comparative example 2
An all-steel tire nylon cord fabric sizing material is prepared from the following raw materials:
100 parts of natural rubber, 37555 parts of carbon black N, 4 parts of aromatic oil, 5 parts of zinc oxide, 2.5 parts of stearic acid, 1.5 parts of antioxidant RD, 0.5 part of antioxidant 6PPD, 801.2 parts of resorcinol, 2 parts of phenolic tackifying resin, 203 parts of sulfur OT, 2 parts of hexamethoxymelamine, 1.2 parts of accelerator TBBS and 0.2 part of antiscorching agent CTP.
The preparation method of the all-steel tire nylon cord fabric rubber material comprises the following steps:
(a) plastic mixing: setting the rotating speed of an internal mixer to be 30rpm, adding natural rubber into the internal mixer, carrying out bolt extraction for 30s after the bolt is pressed for 40s, and then carrying out discharge after the bolt is pressed to 165 ℃; standing for 4h, and then mixing the master batch;
(b) mixing master batch: setting the rotating speed of an internal mixer to be 55rpm, adding all solid materials except sulfur, an accelerator, hexamethoxymelamine and an anti-scorching agent into the internal mixer, carrying out bolt extraction for 30s after bolt pressing, adding a liquid material, carrying out bolt extraction for 5s after the bolt pressing for 30s, and then carrying out discharge after the bolt pressing is carried out to 165 ℃; standing for 8h, and then mixing the mixture for final rubber mixing;
(c) final mixing and milling: setting the rotating speed of an internal mixer to be 20rpm, adding sulfur, an accelerator, hexamethoxymelamine and an anti-scorching agent into the internal mixer, carrying out bolt pressing for 20s, keeping bolt extraction for 5s, carrying out bolt pressing for 30s, keeping bolt extraction for 5s, then carrying out bolt pressing to 100 ℃, discharging to an open mill, and cooling the lower piece to room temperature.
Examples of the experiments
The rubber materials in the examples and the comparative examples of the invention are detected, and the physical performance and vulcanization conditions of the mixed rubber materials are as follows: 151 ℃ for 30 min; no rotor rheology test conditions: 151 ℃ for 60 min; mooney scorch time test conditions: 127 ℃ big rotor; mooney test conditions: ML (1+4)100 ℃; and testing other performance tests according to corresponding national standards. The results are shown in Table 1.
Table 1 sizing material property test results
Comparative example 1 is the nylon cord fabric rubberizing formula of the present all-steel tire, which is mainly reinforced by carbon black and sulfur, the hardness reaches 78, the physical property is good, but the Mooney viscosity is high, the nylon cord fabric rubberizing process can be satisfied only by mixing a section of plastic, a section of three-section masterbatch and a section of final mixing, and the quality problems of non-stick cord fabric, early delamination of the tire and the like are caused because the curtain fabric is easy to frost in the processing process due to the use of a large amount of sulfur.
Comparative example 2 is the nylon cord rubber coating formula of the existing bias tire, the physical properties are good, but the hardness is only 68, the Mooney viscosity is not low, and the nylon cord rubber coating process can be satisfied only by mixing one section of plastic rubber, two sections of masterbatch and one section of final mixing. Meanwhile, the hardness is low, so that the rubber is difficult to match with the hardness of other formula rubber materials, and is not suitable for the design requirement of all-steel tires.
The physical properties of the example 2 are equivalent to those of the comparative example 1, but the Mooney viscosity is reduced by 51 percent, the nylon cord fabric rubber wiping process can be satisfied by only mixing one section of plastic, one section of master batch and one section of final mixing, and the frosting is not easy to cause because the sulfur amount is less. Meanwhile, the scorching time is more than one time higher than that of the comparative example 1 and the comparative example 2, so that scorching and generation of old glue marks are not easy to cause in the processing process.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An all-steel tire nylon cord fabric sizing material is characterized by being mainly prepared from rubber, a compounding agent A and a compounding agent B;
the rubber comprises 80-100 parts by mass of natural rubber;
the compounding agent A comprises the following raw materials in parts by mass: 50-60 parts of carbon black, 5-7 parts of aromatic oil, 8-16 parts of phenolic reinforcing resin and 6-12 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203-4 parts and hexamethylenetetramine 0.8-1.6 parts.
2. An all-steel tire nylon cord fabric rubber compound according to claim 1, characterized in that the natural rubber is 90-100 parts by mass;
the compounding agent A comprises the following raw materials in parts by mass: 52-56 parts of carbon black, 5.5-6.2 parts of aromatic oil, 8-12 parts of phenolic reinforcing resin and 6-10 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-203.5-4 parts and hexamethylenetetramine 0.8-1.2 parts;
preferably, the natural rubber accounts for 100 parts by mass;
the compounding agent A comprises the following raw materials in parts by mass: 55 parts of carbon black, 6 parts of aromatic oil, 14 parts of phenolic reinforcing resin and 10 parts of high styrene resin;
the compounding ingredient B comprises the following raw materials in parts by mass: insoluble sulfur OT-204 parts and hexamethylenetetramine 1.4 parts.
3. An all-steel tire nylon cord fabric rubber compound according to claim 1, wherein the rubber further comprises 1-20 parts by mass of styrene-butadiene rubber;
preferably, the styrene butadiene rubber accounts for 1-10 parts;
preferably, the styrene-butadiene rubber is SBR 1500E.
4. An all-steel tire nylon cord fabric rubber compound according to claim 1, characterized in that the compounding agent A further comprises 4-8 parts by mass of an activating agent;
preferably, the activator comprises zinc oxide and/or stearic acid;
preferably, the compounding agent A further comprises 2-5 parts of an anti-aging agent in parts by mass;
preferably, the antioxidant comprises antioxidant RD.
5. An all-steel tire nylon cord fabric sizing material according to claim 1, characterized in that the compounding agent B further comprises 0.1-1 parts by mass of an accelerator;
preferably, the accelerator comprises an accelerator TBBS;
preferably, the compounding agent B further comprises 0.2-0.5 part of a scorch retarder in parts by mass;
preferably, the scorch retarder comprises the scorch retarder CTP.
6. The all-steel tire nylon cord fabric rubber compound according to any one of claims 1 to 5, wherein the phenolic reinforcing resin comprises a reinforcing-effect polymerized oil NC-360HP and/or tall-oil-modified phenolic reinforcing resin obtained by polymerizing and modifying cashew nut oil as a raw material;
preferably, the high styrene resin is a copolymer of styrene and butadiene, wherein the styrene content is 70 wt% to 85 wt%;
preferably, the carbon black comprises N375 carbon black;
preferably, the natural rubber is 20# standard rubber.
7. The preparation method of the nylon cord rubber for the all-steel tire as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
and (3) mixing the plasticated rubber with the mixture of the accessory ingredient A, and then mixing with the accessory ingredient B for mixing.
8. A method of making an all steel tire nylon cord stock as claimed in claim 7, wherein said rubber mastication comprises the steps of:
adding rubber into an internal mixer, pressing for 35-45 s, extracting the plug for 25-35 s, and pressing the plug to 165-170 ℃ for discharging;
preferably, the rotating speed of the internal mixer is 25-35 rpm;
preferably, the material is discharged and then placed for 4-8 h.
9. A method for preparing nylon cord rubber for all-steel tires according to claim 7, characterized in that, the mixing of the mixture of the masticated rubber and the compounding agent A comprises:
mixing the solid material of the compounding agent A with plasticated rubber, pressing the mixture for 25-30 seconds, adding the liquid material of the compounding agent A after extracting the mixture, keeping the extraction for 4-6 seconds after pressing the mixture for 25-35 seconds, and pressing the mixture to 165-170 ℃ for discharging;
preferably, in the process of mixing the mixture of the plasticated rubber and the compounding agent A, the rotating speed of an internal mixer is 50-60 rpm;
preferably, the material is discharged and then placed for 8-24 h.
10. A method for preparing nylon cord fabric rubber for all-steel tires according to claim 7, characterized in that, the mixing with the compounding agent B for mixing comprises:
the plug is pressed for 15-25 s, the plug is lifted for 4-6 s, the plug is pressed for 25-35 s, the plug is lifted for 4-6 s, and the plug is pressed to 95-105 ℃ and then discharged;
preferably, the rotating speed of the internal mixer is 18-25 rpm in the process of mixing with the compounding agent B for mixing.
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