CN113563562A - Disc-type self-repairing safety tire rubber material and preparation method thereof - Google Patents
Disc-type self-repairing safety tire rubber material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a disc-type self-repairing safety tire rubber material, which belongs to the technical field of high-molecular layered materials, and particularly relates to a tire rubber material prepared by taking butyl rubber, urea-terminated polyurethane liquid rubber and an ethylene-vinyl acetate copolymer as base materials and adding carbonized epoxy polyamide nano short fibers, carbon nano tubes, a softening agent and an antioxidant.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a rubber material for a disc-type self-repairing safety tire and a preparation method thereof.
Background
As automobiles become more popular, accidents of automobiles due to tire safety problems are increasing. In the process of rapid driving of an automobile, the burst moment caused by tire damage affects the life safety of people in the automobile and on the road, so the problem of tire safety is more and more emphasized.
The current automobile wheels mainly have two types, one is an automobile wheel with an inner tube, the other is an automobile wheel without an inner tube, and the current automobile is basically an automobile wheel without an inner tube. The tubeless automobile wheel has good heat dissipation and flexibility, and has the advantages of good air tightness and riding comfort, long time interval of inflation and use and the like, but when the tubeless automobile wheel is punctured by a sharp object, high-pressure gas of the tire can leak outwards at the punctured part because the sharp object is remained in the tire body; when the sharp object pierces the tire and breaks away from the tire, the high-pressure air of the tire leaks rapidly, which can cause the tire burst or rapid leakage of the automobile in the process of high-speed running, and the probability of vehicle damage and human death is high.
In order to improve the use safety of tires and reduce the occurrence of accidents, many organizations begin to research self-sealing liquid glue which is uniformly distributed on the inner surfaces of the tires of the automobile wheels along with the rotation of the automobile wheels, the glue is reacted with oxygen in the air to be solidified so as to achieve the purpose of preventing the tires from leaking, but the liquid glue reacts with the oxygen in the air to form a layer of hard crystals so that the elasticity of the tires is reduced, the performance and the service life of the tires are seriously influenced, and certain potential safety hazards can be generated. The application of solid viscose such as isoprene rubber or butylene rubber makes up the defects of liquid glue, the bulletproof, leakproof and puncture-resistant performances of the automobile tire are obviously improved, but the automobile tire has poor ageing resistance and high temperature resistance, and mainly has a puncture-preventing and puncture-preventing effect on steel nails and a puncture-preventing and puncture-preventing effect on screw nails, oily cement and the like, so that the high polymer rubber material has many difficulties in entering the market. Therefore, it is necessary to develop a material capable of prolonging the service life of the tire, automatically repairing the puncture of the tire, and effectively suppressing the tire leakage and tire burst, so as to improve the safety of the vehicle in running.
Disclosure of Invention
In view of the above, the invention provides a disc-type self-repairing safety tire rubber material, which is solid colloidal, has the advantages of high tensile property, good air tightness, strong cohesiveness, excellent high temperature resistance and low temperature resistance, has good anti-pricking and anti-puncturing effects on steel nails, screws and the like, and can automatically repair a tire when the tire is damaged, thereby avoiding air leakage and tire burst of the tire and improving the running safety of a vehicle.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of ureide-terminated polyurethane liquid rubber is characterized in that polyether polyol, a chain extender and diisocyanate react to obtain an isocyanate-terminated polyurethane prepolymer, and then acetamide benzenesulfonamide and an initiator are added to carry out end capping to obtain the ureide-terminated polyurethane liquid rubber.
It is to be noted that the polyether polyol is any one selected from the group consisting of polyoxypropylene ether triol having a weight average molecular weight of 1000-6000, polytetrahydrofuran ether glycol, tetrahydrofuran-propylene oxide copolyether glycol.
It is noted that the chain extender is a small molecular polyol selected from a mixture of ethambutol and any one of glycerol, trimethylolpropane, trimethylolethane and pentaerythritol, and the mixing mass ratio is 1: 5-8.5.
It is to be noted that the diisocyanate is an aromatic diisocyanate selected from any one of diphenylmethane diisocyanate, toluene diisocyanate, and naphthalene diisocyanate.
And (3) dehydrating the polyether polyol at the temperature of 120-150 ℃ in vacuum, cooling to the temperature below 50 ℃, adding the chain extender and the diisocyanate, uniformly stirring, adding the catalyst, and stirring for reacting for 2.5-4h to obtain the isocyanate-terminated polyurethane prepolymer.
It is noted that the catalyst is selected from any one of stannous octoate, ethyl tin acetate, dibutyl tin dilaurate, di-n-butyl tin diacetate.
It is noted that the mass ratio of the polyether polyol, the chain extender, the diisocyanate and the catalyst is 10:0.5-2:3.5-7: 0.08-0.15.
Adding p-acetamido benzene sulfonamide and a catalyst into the polyurethane prepolymer, stirring for reaction for more than 3.5h, and raising the temperature to 100-110 ℃ for dehydration to obtain the ureide-terminated polyurethane liquid rubber.
It is noted that the adding amount of the p-acetamidobenzenesulfonamide and the catalyst is respectively 10-35% and 0.5-2% of the mass of the polyether polyol.
Polyether glycol, a chain extender and diisocyanate are reacted to prepare an isocyanate-terminated polyurethane prepolymer, the isocyanate-terminated polyurethane prepolymer is modified by acetylamino benzenesulfonamide, amide groups in the acetylamino benzenesulfonamide react with-NCO groups at the end part of the polyurethane prepolymer to generate ureide, so that polyurethane liquid rubber with a cross-linked network structure is prepared, the modified polyurethane liquid rubber material is added into tire rubber material, the rubber material can be rapidly cured, and the cracking phenomenon caused by bubbles generated in the curing process of the rubber material is avoided; the modification treatment of the acetamido benzene sulfonamide enables the polyurethane liquid rubber material to keep good toughness under the condition of higher crosslinking degree, the toughness of the rubber material cannot be reduced, the air tightness of the rubber material can be enhanced by the crosslinking network structure of the liquid rubber material, the adhesive force is high, the rubber material is firmly bonded on the tire and is not easy to fall off, and the tire can be automatically repaired when the tire is damaged; in addition, the heat aging resistance of the rubber compound can be improved, which is probably related to the introduction of ureide groups into the modified polyurethane.
The ureide-terminated polyurethane liquid rubber obtained by the above method.
The ureide-terminated polyurethane liquid rubber is applied to preparation of a disc-covered self-repairing safety tire rubber material.
Said application comprises improving the sealing effect of the glue.
The application also includes improving the heat aging resistance of the compound.
A disc-type self-repairing safety tire rubber material takes butyl rubber, ureide-terminated polyurethane liquid rubber and ethylene-vinyl acetate copolymer as base materials, and carbonized epoxy polyamide nano short fibers are added.
The disc-coated self-repairing safety tire rubber material specifically comprises the following components in parts by weight:
35-50 parts of butyl rubber, 20-30 parts of ureide-terminated polyurethane liquid rubber, 15-30 parts of ethylene-vinyl acetate copolymer, 5-10 parts of softener, 1-3 parts of antioxidant, 6-12 parts of carbonized epoxy polyamide nano short fiber and 3-8 parts of carbon nano tube.
The invention takes butyl rubber, ureide-terminated polyurethane liquid rubber and ethylene-vinyl acetate copolymer as base materials, and adds carbonized epoxy polyamide nano short fibers, carbon nano tubes, a softener and an antioxidant to prepare the disc-type self-repairing safety tire rubber material, overcomes the defects of the existing tire rubber material through reasonable component design, has good air tightness, excellent tensile property, a softening point higher than 180 ℃, is not embrittled or cracked when used at the temperature of-40 ℃, has excellent anti-prick and anti-prick sealing effects at the temperature of-40 ℃ to 110 ℃, overcomes the defect of poor anti-prick and anti-prick effects of the existing tire rubber material on screws, and has great application prospect.
It is noted that the softening agent is selected from any one or more of naphthenic oil, white oil, and polyisobutylene.
It should be noted that the antioxidant is selected from one or more of antioxidant 264, antioxidant 1010, antioxidant 1035, antioxidant 1076 and antioxidant 2246.
The carbonized epoxy polyamide nano short fiber contains calcium hexaluminate and barite in a mass ratio of 2-4.5: 1.
The carbonized epoxy polyamide nano short fiber is prepared by the following method:
1) pretreatment: pretreating calcium hexaluminate powder and barite powder by using ultrasonic waves to obtain activated calcium hexaluminate powder and barite powder;
2) preparing a spinning solution: uniformly mixing the activated calcium hexaluminate and barite with a silane coupling agent, aluminum lignosulfonate, epoxy polyamide and N, N-dimethylacetamide by ultrasonic treatment to obtain a mixed spinning solution;
3) electrostatic spinning: spinning by adopting an electrostatic spinning method to obtain nanofiber non-woven fabric;
4) carbonizing treatment: cutting the non-woven fabric of the nano-fiber, drawing at 225-395 ℃ to carbonize the non-woven fabric of the nano-fiber to obtain carbonized epoxy polyamide nano-staple fiber, and finally crushing the carbonized epoxy polyamide nano-staple fiber to obtain the nano-staple fiber.
It should be noted that the specific operations of step 1) are: respectively putting the calcium hexaluminate and the barite into an ethanol solution with the mass fraction of 10-30% according to the material-to-liquid ratio of 1:12-15, performing ultrasonic treatment for 20-50min, taking out, washing to be neutral, and drying to obtain the activated calcium hexaluminate and the barite.
It is noted that in the step 2), the adding mass ratio of the activated calcium hexaaluminate, the activated barite, the silane coupling agent, the aluminum lignosulfonate, the epoxy polyamide and the N, N-dimethylacetamide is 2-4.5:1:1-2.5:2-3:18-30: 100.
It should be noted that the electrostatic spinning parameters of step 3) are: the inner diameter of the spinning nozzle is 0.25-0.45mm, the voltage is 10-20KV, the flow rate of the spinning solution is 0.1-0.8mL/h, and the temperature of the heating zone is 80-120 ℃.
It should be noted that, in the carbonization treatment in step 4), the draft ratio is 2 to 4.
The invention adds carbonized epoxy polyamide nanometer short fiber into the tyre rubber material, the nanometer short fiber is prepared by mixing calcium hexaluminate and barite after acid solution and ultrasonic pretreatment, and then mixing with epoxy polyamide and utilizing electrostatic spinning, and then carbonizing, the calcium hexaluminate and the barite are wrapped by macromolecule chain of epoxy polyamide, the agglomeration of the calcium hexaluminate and the barite is prevented, the calcium hexaluminate and the barite are added into the rubber material and can be uniformly dispersed in a base material, the defect of reduced mechanical property caused by agglomeration is avoided, the reinforcing effect is achieved, the calcium hexaluminate and the barite have synergistic effect, the compact structure formed in the curing process of the rubber material can be improved, the sealing effect is improved, and the low temperature embrittlement resistance of the rubber material has obvious gain effect, which is probably because the elastic modulus of the carbonized epoxy polyamide nanometer short fiber is larger than that the matrix can bear more load when being stressed, thereby having the effect of toughening and improving the low-temperature embrittlement resistance.
The invention also provides a preparation method of the disc-coated self-repairing safety tire rubber material, which comprises the following steps:
blending butyl rubber and ethylene-vinyl acetate copolymer, stirring for 10-30min, adding ureide-based polyurethane liquid rubber, a softener, an antioxidant, carbonized epoxy polyamide nano short fibers and carbon nano tubes, heating to 80-90 ℃, stirring for 2-3h, heating to 185-220 ℃, stirring for 2-5h, and finally vacuumizing to eliminate bubbles, thereby obtaining the disc-coated self-repairing type safe tire rubber material.
According to the method, the butyl rubber, the ureide-terminated polyurethane liquid rubber and the ethylene-vinyl acetate copolymer are used as base materials, the carbonized epoxy polyamide nano short fibers, the carbon nano tubes, the softening agent and the antioxidant are added to prepare the tire rubber material, the tire rubber material has the advantages of high toughness, high strength, good air tightness, strong cohesiveness, excellent high-temperature resistance and low-temperature resistance by controlling the proportion and processing parameters of the components, the anti-prick and anti-prick effects on steel nails, screws and the like are good, and the tire can be automatically repaired when being damaged, so that the tire is prevented from being leaked and burst, and the safety of vehicle running is improved.
The invention also provides an application of the disc-coated self-repairing safety tire rubber material in preparation of a self-repairing safety tire.
The application comprises the steps of melting the rubber material of the disc-type self-repairing safety tire at the temperature of 200-210 ℃, pumping out the rubber material by using a high-pressure melt pump, spraying out the rubber material from a rubber strip with the diameter of 2-10mm by using a manipulator spray head, covering the rubber strip on the inner surface of the tire to form an airtight layer, treating the inner surface of the tire by using a laser grinding machine in advance, and carrying out rotary cooling.
When the disc-coated self-repairing safety tire rubber material provided by the invention is used, the rubber material is pumped out by a high-pressure melt pump and sprayed out by a mechanical arm spray head, so that the problem that the molecular chain structure is easily damaged when a screw extruder extrudes is solved, the performance of the rubber material is ensured, and the processed self-repairing safety tire can achieve a high-speed test of Y grade.
The invention has the beneficial effects that: according to the invention, butyl rubber, ureide-terminated polyurethane liquid rubber and ethylene-vinyl acetate copolymer are used as base materials, and carbonized epoxy polyamide nano short fibers are added to prepare the disc-coated self-repairing safety tire rubber material, through reasonable component design, the obtained tire rubber material has good air tightness and excellent tensile property, has excellent anti-prick and anti-prick sealing effects at the temperature of-40 ℃ to 110 ℃, and makes up for the defects of the existing tire rubber material; the tire rubber material is added with the ureide-terminated polyurethane liquid rubber, so that the ureide-terminated polyurethane liquid rubber can be uniformly dispersed in a base material, the rubber material can be rapidly cured at normal temperature, cracks are reduced, the air tightness of the rubber material can be enhanced by the cross-linked network structure, and the cohesiveness and the thermal aging resistance are improved; the addition of the carbonized epoxy polyamide nano short fibers in the tire rubber material has a reinforcing effect, can improve the compact structure formed by the rubber material in the curing process, improves the sealing effect, and has an obvious gain effect on the low-temperature embrittlement resistance of the rubber material.
Drawings
FIG. 1 is an infrared spectrum of a liquid ureide-terminated polyurethane rubber of example 1 of the present invention;
FIG. 2 is a schematic representation of the air impermeability test results for the inventive disc-coated self-healing run flat tire compound;
FIG. 3 is a graphical representation of the adhesion test results for the inventive disc-coated self-healing run flat tire compound;
FIG. 4 is a graphical representation of the results of a low temperature resistance test on a compound for a self-healing disk-type run flat tire of the present invention;
FIG. 5 is the thermal aging resistance of the inventive disc-coated self-healing run flat tire compound;
description of reference numerals: in FIG. 1, a represents an isocyanate terminated polyurethane prepolymer and b represents a ureide terminated polyurethane.
Detailed Description
The following describes the technical solution of the present invention in further detail with reference to the detailed description and the accompanying drawings.
Example 1:
a disc-type self-repairing safety tire rubber material comprises the following components in parts by weight:
43 parts of butyl rubber, 24 parts of ureide-terminated polyurethane liquid rubber, 22 parts of ethylene-vinyl acetate copolymer, 8 parts of naphthenic oil, 2 parts of antioxidant 1010, 8 parts of carbonized epoxy polyamide nano short fiber and 5 parts of carbon nano tube.
The preparation method of the rubber material for the disc-type self-repairing safety tire comprises the following steps:
1) preparation of ureide-terminated polyurethane liquid rubber: vacuum dehydrating 10 parts by weight of polyoxypropylene ether triol (the weight average molecular weight is 2000) at 135 ℃, cooling to below 50 ℃, adding 1 part by weight of a mixture of ethambutol and trihydroxyethane (the mixing mass ratio is 1:6.5) and 5.5 parts by weight of diphenylmethane diisocyanate, uniformly stirring, adding 0.1 part by weight of butyl tin dilaurate, and stirring at 600r/min for reacting for 3.5 hours to obtain an isocyanate-terminated polyurethane prepolymer; adding 2.5 parts by weight of p-acetamido benzene sulfonamide and 0.1 part by weight of butyl tin dilaurate into the polyurethane prepolymer, stirring for reaction for 6 hours, and raising the temperature to 105 ℃ for dehydration to obtain ureide-terminated polyurethane liquid rubber;
2) preparing carbonized epoxy polyamide nano short fibers: 3.8 parts by weight of calcium hexaluminate and 1 part by weight of barite are put into 60 parts by weight of 20 percent ethanol solution for ultrasonic treatment for 40min, the ultrasonic frequency is 20kV, and the power density is 0.35W/cm2Taking out calcium hexaluminate and barite, washing to be neutral, and drying at 60 ℃ to obtain activated calcium hexaluminate and barite; ultrasonically dispersing activated calcium hexaluminate and barite in 100 parts by weight of N, N-dimethylacetamide, adding 2 parts by weight of kH560 and 2.4 parts by weight of aluminum lignosulfonate, uniformly stirring, adding 24 parts by weight of epoxy polyamide (with the weight-average molecular weight of 4000), and stirring until the epoxy polyamide and the barite are completely dissolved to obtain a spinning solution; spinning by adopting an electrostatic spinning method to obtain nanofiber non-woven fabric, wherein the inner diameter of a spinning nozzle is 0.3mm, the voltage is 15KV, the flow of spinning solution is 0.5mL/h, and the temperature of a heating zone is 110 ℃; cutting the nanofiber non-woven fabric, and performing the cutting at 340 DEG CDrawing to carbonize the fiber, wherein the drawing multiple is 3 times to obtain carbonized epoxy polyamide nano staple fiber, and finally crushing the carbonized epoxy polyamide nano staple fiber to obtain the fiber;
3) preparing a disc-coated self-repairing safety tire rubber material: according to the formula amount, blending butyl rubber and ethylene-vinyl acetate copolymer, stirring for 20min at 200r/min, then adding ureide-based polyurethane liquid rubber, naphthenic oil, antioxidant 1010, carbonized epoxy polyamide nano short fiber and carbon nano tube, heating to 85 ℃, stirring for 3h, heating to 210 ℃, stirring for 4h, and then vacuumizing to eliminate bubbles, thus obtaining the composite material.
Example 2:
the other disc-type self-repairing safe tire rubber material has basically the same components and preparation method as those in the embodiment 1, and the difference is that the step of modifying the polyurethane prepolymer with acetamido benzene sulfonamide is eliminated in the process of preparing the ureide-terminated polyurethane liquid rubber, namely, the ureide-terminated polyurethane prepolymer liquid rubber is used for replacing the ureide-terminated polyurethane liquid rubber.
Example 3:
the components and the preparation method of the other disc-type self-repairing run-flat tire rubber material are basically the same as those of the rubber material in the embodiment 1, except that the ureide-terminated polyurethane liquid rubber is not added in the rubber material components.
Example 4:
the components and the preparation method of the other rubber material for the disc-type self-repairing run-flat tire are basically the same as those of the rubber material in the embodiment 1, and the difference is that calcium hexaluminate is not added in the process of preparing the carbonized epoxy polyamide nano short fiber.
Example 5:
the components and the preparation method of the other rubber material for the disc-type self-repairing safety tire are basically the same as those of the rubber material in the embodiment 1, and the difference is that barite is not added in the process of preparing the carbonized epoxy polyamide nano short fiber.
Example 6:
the components and the preparation method of the other disc-type self-repairing safety tire rubber material are basically the same as those of the rubber material in the embodiment 1, and the difference is that calcium hexaluminate and barite are not added in the process of preparing the carbonized epoxy polyamide nano short fiber.
Example 7:
the components and the preparation method of the other rubber material for the disc-type self-repairing run-flat tire are basically the same as those of the rubber material in the embodiment 1, except that the carbonized epoxy polyamide nano short fiber is not added.
Test example 1:
infrared spectrum test:
an attenuated total reflection test is carried out on the sample by adopting a Nexus-870 Fourier transform infrared spectrometer (ATR), and the wavelength range is 4000-500cm-1Scan 32 times with resolution of 2cm-1。
The isocyanate terminated polyurethane prepolymer and the ureide terminated polyurethane liquid rubber obtained in example 1 were subjected to the above-mentioned tests, and the infrared spectrum thereof was found to be as shown in FIG. 1.
As can be seen from the graph of FIG. 1, the curve a is 2965cm-1、2865cm-1The vibration peaks are 1700cm-1Stretching vibration peak at position of carbonyl of 1537cm-1Flexural vibration peak at N-H, 2270cm-1Is located at the stretching vibration peak of-NCO; and in curve b, 2270cm-1The characteristic absorption peak at-NCO disappeared at 1714cm-1、1658cm-1A new absorption peak appears at, known as 1710--1At 1650cm, where is the C ═ O peak of ureido group-1The stretching vibration peak of hydrogen bonded C ═ O of ureido on the left and right shows that-NCO reacts with amide group to form ureido group, and the curve b is 1180cm-1、1058cm-1、630cm-1The absorption peak of sulfonic acid group appears, and the results show that the acetamido benzene sulfonamide successfully reacts with-NCO at the end of polyurethane to complete ureide end capping.
Test example 2:
and (3) testing tensile property:
the tensile properties were tested with reference to the standard GB/T528-2009 with the test parameters: the sample size is 100mm multiplied by 10mm multiplied by 3mm, the stretching rate is 500mm/min, the stretching amount is 1mm, the temperature is 25 ℃, and the relative humidity is 50%.
The above tests were performed on the compounds for a self-healing, disk-coated run-flat tire prepared in examples 1-7, and the results of tensile strength, elongation at break, and 100% stress at elongation at break are shown in Table 1.
TABLE 1 tensile Properties
| Examples | Tensile Strength (MPa) | Elongation at Break (%) | 100% stress at definite elongation (MPa) |
| 1 | 18.52 | 785.7 | 1.65 |
| 2 | 18.21 | 670.3 | 2.37 |
| 3 | 17.83 | 758.5 | 1.79 |
| 4 | 14.03 | 611.7 | 3.57 |
| 5 | 14.57 | 640.4 | 3.31 |
| 6 | 13.81 | 560.3 | 4.15 |
| 7 | 12.13 | 524.1 | 4.88 |
From the analysis of the tensile strength data in Table 1, it can be seen that the differences in tensile strength between examples 1-3 are small, indicating that the influence of both the polyurethane liquid rubber and the acetamide-based benzenesulfonamide-modified polyurethane liquid rubber on the strength of the tire compound is small; the tensile strength of examples 4-6 is lower than that of example 1 and examples 6 and 7 are lower than those of examples 4 and 5, which shows that the tensile strength of the tire compound is improved more by adding certain amounts of calcium hexaaluminate and barite to the carbonized epoxy polyamide nano-staple fiber.
From the tensile elongation at break, 100% tensile stress data analysis in table 1, it can be seen that the tensile stress of example 2 is higher than that of examples 1 and 3, and the tensile elongation at break is lower than that of examples 1 and 3, indicating that the addition of unmodified liquid polyurethane rubber decreases the toughness of the tire compound; the tensile elongation of the examples 4-6 is lower than that of the example 1, and the tensile stress is higher than that of the example 1, which shows that the effect of simultaneously adding certain amounts of calcium hexaaluminate and barite to the carbonized epoxy polyamide nano-short fiber on the toughness gain of the tire compound is better.
Test example 3:
and (3) air tightness performance test:
the test is carried out based on the test principle of a pressure difference method, oxygen is used as test gas, the test temperature is 23 ℃, the high-pressure is 0.1MPa, the low-pressure is lower than 10Pa, the volume of the gas penetrating through the test sample in unit time and unit area is tested, and the thickness of the test sample is 1 mm.
The above tests were performed on the compounds for self-healing, disk-covered run-flat tires prepared in examples 1-7, and the results of gas transmission are shown in FIG. 2.
As can be seen from the data analysis in fig. 2, the gas permeation rates of the tire compounds obtained in examples 2 and 3 are higher than those of example 1, and the gas permeation rate of example 3 is higher than that of example 2, which shows that compared with the polyurethane liquid rubber, the addition of the polyurethane liquid rubber modified by p-acetamidobenzenesulfonamide is more beneficial to reducing the gas permeation rate of the tire compound and improving the air tightness; the gas permeability of examples 4-7 is higher than that of example 1, and examples 6 and 7 are higher than examples 4 and 5, and example 7 is higher than example 6, which shows that the air impermeability of the tire compound is improved by adding the carbonized epoxy polyamide nano-staple fiber containing calcium hexaaluminate and barite, and the air impermeability of the tire compound is improved by adding a certain amount of calcium hexaaluminate and barite to the carbonized epoxy polyamide nano-staple fiber.
Test example 4:
adhesion:
melting the sample at 210 deg.C, pumping out with high pressure melt pump, spraying with manipulator nozzle with 2-10mm diameter rubber strip, covering on the inner surface of the tire, cooling, peeling with DCS-500 universal tester, and testing the adhesive force.
The adhesion results obtained from the above tests on the compounds for self-healing and disk-coated run-flat tires prepared in examples 1-7 are shown in FIG. 3.
From the data analysis in fig. 3, it can be seen that the adhesive force of examples 1 and 5-7 is higher than 600N and the difference is small, which indicates that the tire compound provided by the present invention has good adhesion, and the addition of the carbonized epoxy polyamide nano-staple fibers has no significant influence on the adhesion of the tire compound; the adhesion of example 2 is lower than that of example 1, and the adhesion of example 3 is lower than that of example 2, which shows that the polyurethane liquid rubber is more favorable for improving the adhesion of the tire compound after being modified by acetamidobenzenesulfonamide.
Test example 5:
low temperature resistance:
after the disc-type self-repairing safety tire rubber materials prepared in examples 1-7 were placed in a refrigerator at-40 ℃ for 48 hours, the elongation at break was measured, and the low-temperature resistance of the rubber materials was evaluated by the reduction rate of the elongation at break. The results of measuring the tensile elongation decrease rate are shown in FIG. 4.
As can be seen from the data analysis in FIG. 4, the elongation at break of examples 1-3 is less than 10%, and the difference is small, which indicates that no matter the polyurethane liquid rubber or the polyurethane liquid rubber modified by acetamido benzenesulfonamide has no significant influence on the low temperature resistance of the tire rubber material, and the tire rubber material provided by the present invention has good low temperature embrittlement resistance, and the elongation at break at low temperature does not significantly decrease; the tensile elongation reduction of examples 4-7 is higher than that of example 1, and examples 6 and 7 are higher than examples 4 and 5, and example 7 is higher than example 6, which shows that the effect of the addition of certain amounts of calcium hexaluminate and barite to the carbonized epoxy polyamide nano-staple fibers is better for the low temperature resistance of the tire compound than the carbonized epoxy polyamide nano-staple fibers containing no calcium hexaluminate and barite.
Test example 6:
thermal aging resistance:
after the disc-type self-repairing safety tire rubber materials prepared in the examples 1-7 are placed in a heat preservation box at the temperature of 110 ℃ for 48 hours, the elongation at break of the rubber materials is tested, and the thermal aging resistance is evaluated by using the reduction rate of the elongation at break. The results of measuring the tensile elongation decrease rate are shown in FIG. 5.
From the data analysis in fig. 5, it can be seen that the tensile elongation reduction rate of examples 1, 4-7 is less than 7.5%, and the difference is small, which indicates that the addition of the carbonized epoxy polyamide nano-staple fibers has little influence on the thermal aging resistance of the tire compound; the tensile elongation rate reduction rate of the examples 2 and 3 is higher than that of the example 1, and the tensile elongation rate reduction rate of the example 3 is higher than that of the example 2, which shows that the polyurethane liquid rubber is more favorable for improving the heat aging resistance of the tire compound after being modified by the acetamido benzene sulfonamide.
In conclusion, the invention provides a solid disc-coated self-repairing safety tire rubber material which has the advantages of high tensile property, good air tightness, strong adhesion, softening point higher than 180 ℃, no embrittlement and cracking when used at the temperature of-40 ℃, excellent anti-prick and anti-prick sealing effects at the temperature of-40 ℃ to 110 ℃, overcomes the defect of poor anti-prick and anti-prick effects of the conventional tire rubber material on screws, and has great application prospect.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A preparation method of ureide-terminated polyurethane liquid rubber is characterized in that,
polyether polyol, a chain extender and diisocyanate react to obtain an isocyanate-terminated polyurethane prepolymer, and then acetamide-based benzenesulfonamide and an initiator are added to carry out end capping to obtain the isocyanate-terminated polyurethane prepolymer;
and the addition amount of the p-acetamidobenzenesulfonamide is 10-35% of the weight of the polyether polyol.
2. The method as set forth in claim 1, wherein the chain extender is a small molecular polyol selected from the group consisting of a mixture of ethambutol and any one of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol in a mixing mass ratio of 1: 5-8.5.
3. Use of the ureide-terminated polyurethane liquid rubber obtained by the method of claim 1 or 2 in the preparation of a disc-covered self-healing run-flat tire compound, wherein the use comprises:
the sealing effect of the rubber material is improved; and/or
The heat aging resistance of the rubber material is improved.
4. A disc-type self-repairing run-flat tire compound, which is characterized by comprising the ureide-terminated polyurethane liquid rubber obtained by the method of claim 1 or 2.
5. The disc-coated self-repairing safety tire rubber material as claimed in claim 4, wherein butyl rubber, the ureide-terminated polyurethane liquid rubber as claimed in claim 1 or 2, and ethylene-vinyl acetate copolymer are used as base materials, and carbonized epoxy polyamide nano-short fibers are further added.
6. The disc-coated self-repairing safety tire rubber material as claimed in claim 5, wherein the carbonized epoxy polyamide nano-staple fibers comprise calcium hexaluminate and barite in a mass ratio of 2-4.5: 1.
7. The disc-coated self-repairing safety tire compound according to claim 5 or 6, wherein the carbonized epoxy polyamide nano-staple fiber is prepared by the following method:
1) pretreatment: pretreating calcium hexaluminate powder and barite powder by using ultrasonic waves to obtain activated calcium hexaluminate powder and barite powder;
2) preparing a spinning solution: uniformly mixing the activated calcium hexaluminate and barite with a silane coupling agent, aluminum lignosulfonate, epoxy polyamide and N, N-dimethylacetamide by ultrasonic treatment to obtain a mixed spinning solution;
3) electrostatic spinning: spinning by adopting an electrostatic spinning method to obtain nanofiber non-woven fabric;
4) carbonizing treatment: cutting the non-woven fabric of the nano-fiber, drawing at 225-395 ℃ to carbonize the non-woven fabric of the nano-fiber to obtain carbonized epoxy polyamide nano-staple fiber, and finally crushing the carbonized epoxy polyamide nano-staple fiber to obtain the nano-staple fiber.
8. The process for preparing a reel on self-healing run-flat tire compound as claimed in any one of claims 4 to 7, comprising:
blending butyl rubber and ethylene-vinyl acetate copolymer, stirring for 10-30min under 5-10MPa, adding ureide-based polyurethane liquid rubber, a softening agent, an antioxidant, carbonized epoxy polyamide nano short fibers and carbon nano tubes, heating to 80-90 ℃, stirring for 2-3h, heating to 185-220 ℃, stirring for 2-5h, and finally vacuumizing to eliminate bubbles, thereby obtaining the disc-coated self-repairing safe tire rubber material.
9. The method of claim 8, wherein the electrospinning parameters are: the inner diameter of the spinning nozzle is 0.25-0.45mm, the voltage is 10-20KV, the flow rate of the spinning solution is 0.1-0.8mL/h, and the temperature of the heating zone is 80-120 ℃.
10. The application of the disc-type self-repairing safety tire rubber material as claimed in any one of claims 4 to 7 in the preparation of the self-repairing safety tire is characterized in that after the disc-type self-repairing safety tire rubber material is melted at the temperature of 200 ℃ and 210 ℃, the rubber material is pumped out by a high-pressure melt pump, the rubber material is sprayed out by a mechanical arm nozzle from a rubber strip with the diameter of 2-10mm and is covered on the inner surface of the tire to form an airtight layer, the inner surface of the tire is treated by a laser grinding machine in advance, and the tire is obtained after rotating and cooling.
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| CN116396605A (en) * | 2023-04-12 | 2023-07-07 | 无锡安睿驰科技有限公司 | New energy automobile tire puncture-preventing disc-covered self-repairing sealing material and preparation method thereof |
| CN116656115A (en) * | 2023-06-13 | 2023-08-29 | 山东华盛橡胶有限公司 | Self-sealing mixed rubber without affecting uniformity of tire, preparation method thereof and tire |
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| CN116396605A (en) * | 2023-04-12 | 2023-07-07 | 无锡安睿驰科技有限公司 | New energy automobile tire puncture-preventing disc-covered self-repairing sealing material and preparation method thereof |
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| CN116656115A (en) * | 2023-06-13 | 2023-08-29 | 山东华盛橡胶有限公司 | Self-sealing mixed rubber without affecting uniformity of tire, preparation method thereof and tire |
| CN116656115B (en) * | 2023-06-13 | 2024-01-23 | 山东华盛橡胶有限公司 | Self-sealing mixed rubber without affecting uniformity of tire, preparation method thereof and tire |
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