Self-repairing mute tire and preparation method thereof

Abstract

The invention discloses a self-repairing mute tire and a preparation method thereof, and relates to the technical field of tires, the self-repairing mute tire comprises a tire body, and a self-repairing rubber layer and a mute material which are sequentially attached to the inner wall of the tire body from inside to outside; the self-repairing adhesive layer is prepared from the following components: epichlorohydrin rubber, acrylate rubber, a rosinyl phenyl phosphine oxide isoxazolyl functional polymer, 4, 4-chloroformyl phenyl ether, a catalyst, 2, 2-bis [4-(4-aminophenoxy) phenyl]-1, 1, 1, 3, 3, 3-hexafluoropropane, trithiocyanuric acid, a filler, an accelerant TMTD (Tetramethylthiuram Disulfide) and an auxiliary agent; the rosinyl phenyl phosphine oxide isoxazolyl functional polymer comprises structural units introduced through a condensation polymerization reaction of the following monomers: glycerol triabietate, bis (4-carboxyl phenyl) phenyl phosphine oxide and 3, 5-isoxazoledicarboxylic acid. The tire is remarkable in self-repairing effect, good in mute performance, sufficient in performance stability and long in service life.

Description

Technical Field

[0001] This invention relates to the field of tire technology, and in particular to a self-sealing quiet tire and its preparation method. Background Technology

[0002] In recent years, the automotive industry has developed rapidly, and consumers have increasingly higher demands for vehicle comfort and driving safety. Tire noise has always been a significant factor affecting vehicle comfort, so consumers are becoming increasingly discerning about tire quietness when purchasing tires. During driving, a puncture requires changing to a spare tire or waiting for roadside assistance; in more serious cases, it can lead to tire blowouts or even rollovers, severely impacting passenger safety. It is in this context that self-repairing quiet tires have emerged, attracting widespread attention within the industry.

[0003] One of the more mature methods in the existing self-sealing quiet tire manufacturing process is to attach a layer of sound insulation / absorption material (such as polyurethane sound insulation cotton) to the inner wall of the tire using an external adhesive. However, due to unreasonable formulation of the external adhesive, the sound insulation material of the finished quiet tire is easy to fall off, resulting in limited sound insulation effect, poor performance stability, and unsatisfactory self-sealing performance.

[0004] To address the aforementioned issues, patent application CN111016549A discloses a puncture-resistant, self-healing, repair-free, quiet tire and its processing method. The tire body includes sidewalls on both sides of the tread and a tread extending circumferentially to form a ring. A bead is located on the sidewall where the tire is mounted to the rim. The tread includes an outer surface in contact with the ground and an inner surface in contact with the air filling the tire. Between the inner and outer surfaces, from the inside out, are sequentially formed a rubber coating, an airtight layer for sealing, a belt layer composed of multiple steel wires, and a crown belt layer composed of fiber cords. Noise-reducing components are installed on the tread surface close to the inner surface. The ring-shaped self-healing rubber on the inner surface of the tread achieves puncture resistance, self-healing, and repair-free functionality, while the strip-shaped sound-absorbing and noise-reducing components mounted on the inner surface of the self-healing rubber further enhance noise reduction performance. However, it does not limit the specific self-healing rubber formulation; if the formulation is unsuitable, good self-healing and stable noise reduction effects cannot be achieved.

[0005] It is evident that developing a self-repairing, quiet tire with significant self-healing effect, good noise reduction performance, sufficient performance stability, and long service life, as well as its preparation method, meets market demand, has broad market value and application prospects, and is of great significance to promoting the development of the quiet tire field. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a self-repairing quiet tire with significant self-healing effect, good noise reduction performance, sufficient performance stability, and long service life, as well as a method for preparing the tire.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a self-repairing quiet tire, comprising a tire body and a self-repairing adhesive layer and a noise-reducing material sequentially bonded to the inner wall of the tire body from the inside out; the self-repairing adhesive layer comprises the following components in parts by weight: 20-30 parts of chlorohydrin rubber, 20-30 parts of acrylate rubber, 10-15 parts of rosin-based phenylphosphine oxide isoxazole functional polymer, 1-3 parts of 4,4-chloroformylphenyl ether, 1-2 parts of catalyst, 2-4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 0.8-1.2 parts of trithiocyanate, 15-25 parts of filler, and TMTD accelerator. 0.3-0.6 parts, 1-3 parts of additives; the rosin-based phenylphosphine oxide-isoxazole functional polymer includes structural units introduced by the following monomers through polycondensation reaction: trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isoxazole dicarboxylic acid.

[0008] Preferably, the additive is a mixture formed by mixing an anti-aging agent, an environmentally friendly plasticizer, a softener, and an anti-scorching agent in a mass ratio of 1:(1-2):(0.8-1.2):0.5.

[0009] Preferably, the anti-aging agent is NBC; the environmentally friendly plasticizer is epoxidized soybean oil; the softener is at least one of naphthenic oil and white oil; and the anti-scorching agent is CTP.

[0010] Preferably, the filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:(8-12); the particle size of the calcium carbonate is 400-800 mesh; and the particle size of the magnesium oxide is 500-1000 mesh.

[0011] Preferably, the catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:(3-5).

[0012] Preferably, the preparation method of the rosin-based phenylphosphine oxide-isoxazole-based functional polymer includes the following steps: adding trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, and catalyst to a high-boiling-point solvent, stirring at 110-130°C for 3-5 hours to obtain a reaction solution, then transferring the reaction solution to a high-pressure reactor, replacing the air in the reactor with an inert gas, and then stirring the reaction at 145-150°C under normal pressure for 3-5 hours, then reducing the pressure to 50-100 Pa, raising the temperature to 240-250°C, and stirring the reaction under temperature and pressure for 18-24 hours, after the reaction is completed, cooling to room temperature, precipitating in water, washing the precipitated polymer with ethanol 3-6 times, and finally drying in a vacuum dryer at 85-95°C to constant weight to obtain the rosin-based phenylphosphine oxide-isoxazole-based functional polymer.

[0013] Preferably, the molar ratio of trirosinic acid glyceride, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, catalyst, and high-boiling solvent is 1:0.5:0.5:(0.8-1.2):(6-10).

[0014] Preferably, the catalyst is at least one of tetrabutyl titanate, p-toluenesulfonic acid, and antimony acetate; the high-boiling-point solvent is dimethyl sulfoxide; and the inert gas is any one of nitrogen, helium, neon, and argon.

[0015] Preferably, the acrylate rubber is ACM with the grade AR74, a product of Zeon Corporation of Japan.

[0016] Preferably, the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber with the grade T-55.

[0017] Preferably, the sound-absorbing material is sound-absorbing cotton; the sound-absorbing cotton has a density of 20 kg / m³. 3 -40kg / m 3 Polyurethane foam.

[0018] Another object of the present invention is to provide a method for preparing the self-sealing quiet tire, comprising the following steps: Step S1: Perform high-energy laser cleaning on the inner wall surface of the tire body; Step S2: Add chlorohydrin rubber, acrylate rubber and rosin-based phenylphosphine oxide isoxazole functional polymer to a two-roll mill for plasticizing and rolling. Then add other components of the self-healing adhesive layer and mix for 8-12 minutes. Next, add the rubber compound to solvent oil, stir evenly, and apply it to the inner wall surface of the tire body. Then attach the sound-absorbing material to the surface of the adhesive layer and cure at 150-160℃ for 10-20 minutes.

[0019] Preferably, the power of the high-energy laser cleaning in step S1 is between 200 and 500 kW.

[0020] Preferably, the solvent oil in step S2 is No. 120 solvent oil; the mass ratio of the adhesive to the solvent oil is 2:1.

[0021] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The method for preparing self-repairing silent tires disclosed in this invention can be achieved using conventional equipment and production lines. It requires less capital investment, consumes less energy, has a simple process, is easy to operate and control, has high preparation efficiency and finished product qualification rate, is suitable for continuous large-scale production, and has high promotion and application value.

[0022] (2) The self-repairing quiet tire disclosed in this invention includes a tire body and a self-repairing rubber layer and a noise-reducing material that are sequentially bonded to the inner wall of the tire body from the inside out. Through this structural design, the tire structure can be made more stable, and at the same time has the functions of self-repair and noise reduction. The self-repairing rubber layer is made of the following components in parts by weight: 20-30 parts of chlorohydrin rubber, 20-30 parts of acrylate rubber, 10-15 parts of rosin-based phenyl oxyphosphine oxide isoxazole functional polymer, 1-3 parts of 4,4-chloroformyl phenyl ether, 1-2 parts of catalyst, 2-4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 0.8-1.2 parts of trithiocyanate, 15-25 parts of filler, and TMTD accelerator. 0.3-0.6 parts of additives and 1-3 parts of auxiliaries; through the synergistic effect of the components, the resulting tire exhibits significant self-healing properties, excellent noise reduction, high performance stability, and long service life. The self-healing rubber layer incorporates chlorohydrin rubber, acrylate rubber, rosin-based, phenylphosphine oxide-based, isoxazole-based, and fluorinated phenyl ether structures. These structures, under the combined effects of electronic, steric, and conjugation effects, result in excellent self-healing performance, superior weather resistance, and strong adhesion, thereby effectively improving noise reduction and stability. This leads to more stable vehicle operation, lower noise levels, and higher overall stability.

[0023] (3) The self-repairing quiet tire disclosed in this invention comprises a rosin-based phenylphosphine oxide-isoxazole functional polymer containing structural units introduced through a polycondensation reaction of the following monomers: trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isoxazole dicarboxylic acid. The simultaneous introduction of the rosin structure, phenylphosphine oxide group, and isoxazole structure, under the combined effects of electronic effects, steric hindrance effects, and conjugation effects, results in a more significant self-repairing effect, better quietness, greater performance stability, and longer service life for the manufactured product. Detailed Implementation

[0024] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0025] Example 1 A self-sealing, quiet tire includes a tire body and a self-healing adhesive layer and a noise-reducing material sequentially bonded to the inner wall of the tire body from the inside out. The self-healing adhesive layer is composed of the following components in parts by weight: 20 parts of chlorohydrin rubber, 20 parts of acrylate rubber, 10 parts of rosin-based phenylphosphine oxide isoxazole functional polymer, 1 part of 4,4-chloroformylphenyl ether, 1 part of catalyst, 2 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 0.8 parts of trithiocyanate, 15 parts of filler, 0.3 parts of accelerator TMTD, and 1 part of additive. The rosin-based phenylphosphine oxide isoxazole functional polymer comprises structural units introduced by the following monomers through a polycondensation reaction: trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isooxazole dicarboxylic acid.

[0026] The additive is a mixture of an anti-aging agent, an environmentally friendly plasticizer, a softener, and an anti-scorching agent in a mass ratio of 1:1:0.8:0.5; the anti-aging agent is NBC; the environmentally friendly plasticizer is epoxidized soybean oil; the softener is naphthenic oil; and the anti-scorching agent is CTP.

[0027] The filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:8; the calcium carbonate has a particle size of 400 mesh; the magnesium oxide has a particle size of 500 mesh; and the catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:3.

[0028] The preparation method of the rosin-based phenylphosphine oxide-isoxazole-based functional polymer includes the following steps: adding trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, and a catalyst to a high-boiling-point solvent, stirring at 110°C for 3 hours to obtain a reaction solution, then transferring the reaction solution to a high-pressure reactor, replacing the air in the reactor with an inert gas, and then stirring the reaction at 145°C under normal pressure for 3 hours, then reducing the pressure to 50 Pa, raising the temperature to 240°C, and maintaining the temperature and pressure while stirring for 18 hours. After the reaction was completed, the mixture was cooled to room temperature and precipitated in water. The precipitated polymer was then washed three times with ethanol and finally dried at 85°C under vacuum to constant weight to obtain a rosin-based phenylphosphine oxide-isoxazole functional polymer. The molar ratio of trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, catalyst, and high-boiling solvent was 1:0.5:0.5:0.8:6. The catalyst was tetrabutyl titanate; the high-boiling solvent was dimethyl sulfoxide; and the inert gas was nitrogen. The molecular weight (M) of the obtained functional polymer was measured by GPC. n =15170 g / mol, M W / M n =1.384; Through elemental analysis and weight change calculations, the molar ratio of the structural units introduced by trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isoxazole dicarboxylic acid in the functional polymer is approximately 1:0.5:0.5, which is the same as the theoretical value.

[0029] The acrylate rubber is ACM, brand AR74, a product of Zeon Corporation of Japan; the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber, brand T-55; the sound-absorbing material is sound-absorbing cotton; the sound-absorbing cotton has a density of 30 kg / m³. 3 Polyurethane foam.

[0030] A method for preparing the self-sealing quiet tire includes the following steps: Step S1: Perform high-energy laser cleaning on the inner wall surface of the tire body; Step S2: Add chlorohydrin rubber, acrylate rubber and rosin-based phenylphosphine oxide isoxazole functional polymer to a two-roll mill for plasticizing and rolling. Then add other components of the self-healing adhesive layer and mix for 8 minutes. Next, add the rubber compound to solvent oil, stir evenly, and apply it to the inner wall surface of the tire body. Then attach the sound-dampening material to the surface of the adhesive layer and cure at 150°C for 10 minutes.

[0031] The power of the high-energy laser cleaning described in step S1 is 200 kW.

[0032] The solvent oil mentioned in step S2 is No. 120 solvent oil; the mass ratio of the adhesive to the solvent oil is 2:1.

[0033] Example 2 A self-healing, quiet tire includes a tire body and a self-healing rubber layer and a noise-reducing material sequentially bonded to the inner wall of the tire body from the inside out. The self-healing rubber layer is composed of the following components in parts by weight: 23 parts of chlorohydrin rubber, 22 parts of acrylate rubber, 11 parts of rosin-based phenylphosphine oxide isoxazole functional polymer, 1.5 parts of 4,4-chloroformylphenyl ether, 1.2 parts of catalyst, 2.5 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 0.9 parts of trithiocyanate, 17 parts of filler, 0.4 parts of accelerator TMTD, and 1.5 parts of additives. The rosin-based phenylphosphine oxide isoxazole functional polymer comprises structural units introduced by the following monomers through a polycondensation reaction: trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isooxazole dicarboxylic acid.

[0034] The additive is a mixture of anti-aging agent, environmentally friendly plasticizer, softener, and anti-scorching agent in a mass ratio of 1:1.3:0.9:0.5; the anti-aging agent is NBC; the environmentally friendly plasticizer is epoxidized soybean oil; the softener is white oil; and the anti-scorching agent is CTP.

[0035] The filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:9; the calcium carbonate has a particle size of 500 mesh; the magnesium oxide has a particle size of 600 mesh; and the catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:3.5.

[0036] The preparation method of the rosin-based phenylphosphine oxide-isoxazole-based functional polymer includes the following steps: adding trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, and a catalyst to a high-boiling-point solvent, stirring at 115°C for 3.5 hours to obtain a reaction solution, then transferring the reaction solution to a high-pressure reactor, replacing the air in the reactor with an inert gas, and then stirring the reaction at 147°C under normal pressure for 3.5 hours, then reducing the pressure to 60 Pa, raising the temperature to 242°C, and maintaining the temperature and pressure while stirring the reaction. After 20 hours of reaction, the mixture was cooled to room temperature, precipitated in water, and washed four times with ethanol. Finally, it was dried at 87°C under vacuum to constant weight to obtain a rosin-based phenylphosphine oxide-isoxazole functional polymer. The molar ratio of trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, catalyst, and high-boiling solvent was 1:0.5:0.5:0.9:7. The catalyst was p-toluenesulfonic acid; the high-boiling solvent was dimethyl sulfoxide; and the inert gas was helium.

[0037] The acrylate rubber is ACM, brand AR74, a product of Zeon Corporation of Japan; the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber, brand T-55; the sound-absorbing material is sound-absorbing cotton; the sound-absorbing cotton has a density of 30 kg / m³. 3 Polyurethane foam.

[0038] A method for preparing the self-sealing quiet tire includes the following steps: Step S1: Perform high-energy laser cleaning on the inner wall surface of the tire body; Step S2: Add chlorohydrin rubber, acrylate rubber and rosin-based phenylphosphine oxide isoxazole functional polymer to a two-roll mill for plasticizing and rolling. Then add other components of the self-healing adhesive layer and mix for 9 minutes. Next, add the rubber compound to solvent oil, stir evenly, and apply it to the inner wall surface of the tire body. Then attach the sound-absorbing material to the surface of the adhesive layer and cure at 153°C for 12 minutes.

[0039] The power of the high-energy laser cleaning in step S1 is 300 kW; the solvent oil in step S2 is No. 120 solvent oil; the mass ratio of the adhesive to the solvent oil is 2:1.

[0040] Example 3 A self-healing, quiet tire includes a tire body and a self-healing rubber layer and a noise-reducing material sequentially bonded to the inner wall of the tire body from the inside out. The self-healing rubber layer is composed of the following components in parts by weight: 25 parts of chlorohydrin rubber, 25 parts of acrylate rubber, 13 parts of rosin-based phenylphosphine oxide isoxazole functional polymer, 2 parts of 4,4-chloroformylphenyl ether, 1.5 parts of catalyst, 3 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1 part of trithiocyanate, 20 parts of filler, 0.45 parts of accelerator TMTD, and 2 parts of additives. The rosin-based phenylphosphine oxide isoxazole functional polymer comprises structural units introduced by the following monomers through a polycondensation reaction: trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isooxazole dicarboxylic acid.

[0041] The additive is a mixture of an anti-aging agent, an environmentally friendly plasticizer, a softener, and an anti-scorching agent in a mass ratio of 1:1.5:1:0.5; the anti-aging agent is NBC; the environmentally friendly plasticizer is epoxidized soybean oil; the softener is naphthenic oil; and the anti-scorching agent is CTP.

[0042] The filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:10; the calcium carbonate has a particle size of 600 mesh; the magnesium oxide has a particle size of 800 mesh; and the catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:4.

[0043] The preparation method of the rosin-based phenylphosphine oxide-isoxazole-based functional polymer includes the following steps: adding trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, and a catalyst to a high-boiling-point solvent, stirring at 120°C for 4 hours to obtain a reaction solution, then transferring the reaction solution to a high-pressure reactor, replacing the air in the reactor with an inert gas, and then stirring the reaction at 148°C under normal pressure for 4 hours, then reducing the pressure to 80 Pa, raising the temperature to 245°C, and maintaining the temperature and pressure while stirring the reaction. After 21 hours of reaction, the mixture was cooled to room temperature, precipitated in water, and washed five times with ethanol. Finally, it was dried at 90°C under vacuum to constant weight to obtain a rosin-based phenylphosphine oxide-isoxazole functional polymer. The molar ratio of trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, catalyst, and high-boiling solvent was 1:0.5:0.5:1:8. The catalyst was antimony acetate, the high-boiling solvent was dimethyl sulfoxide, and the inert gas was neon.

[0044] The acrylate rubber is ACM, brand AR74, a product of Zeon Corporation of Japan; the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber, brand T-55; the sound-absorbing material is sound-absorbing cotton; the sound-absorbing cotton has a density of 30 kg / m³. 3 Polyurethane foam.

[0045] A method for preparing the self-sealing quiet tire includes the following steps: Step S1: Perform high-energy laser cleaning on the inner wall surface of the tire body; Step S2: Add chlorohydrin rubber, acrylate rubber and rosin-based phenylphosphine oxide isoxazole functional polymer to a two-roll mill for plasticizing and rolling. Then add other components of the self-healing adhesive layer and mix for 10 minutes. Next, add the rubber compound to solvent oil, stir evenly, and apply it to the inner wall surface of the tire body. Then attach the sound-absorbing material to the surface of the adhesive layer and cure at 155°C for 15 minutes.

[0046] The power of the high-energy laser cleaning in step S1 is 350 kW; the solvent oil in step S2 is No. 120 solvent oil; the mass ratio of the adhesive to the solvent oil is 2:1.

[0047] Example 4 A self-sealing, quiet tire includes a tire body and a self-healing rubber layer and a noise-reducing material sequentially bonded to the inner wall of the tire body from the inside out. The self-healing rubber layer is composed of the following components in parts by weight: 28 parts of chlorohydrin rubber, 28 parts of acrylate rubber, 14 parts of rosin-based phenylphosphine oxide isoxazole functional polymer, 2.5 parts of 4,4-chloroformylphenyl ether, 1.8 parts of catalyst, 3.5 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1.1 parts of trithiocyanate, 23 parts of filler, 0.55 parts of accelerator TMTD, and 2.5 parts of additives. The rosin-based phenylphosphine oxide isoxazole functional polymer comprises structural units introduced by the following monomers through a polycondensation reaction: trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isooxazole dicarboxylic acid.

[0048] The additives are a mixture of an anti-aging agent, an environmentally friendly plasticizer, a softener, and an anti-scorching agent in a mass ratio of 1:1.8:1.1:0.5; the anti-aging agent is NBC; the environmentally friendly plasticizer is epoxidized soybean oil; the softener is at least one of naphthenic oil and white oil; the anti-scorching agent is CTP; the filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:11; the calcium carbonate has a particle size of 750 mesh; the magnesium oxide has a particle size of 900 mesh; and the catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:4.5.

[0049] The preparation method of the rosin-based phenylphosphine oxide-isoxazole-based functional polymer includes the following steps: adding trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, and a catalyst to a high-boiling-point solvent, stirring at 125°C for 4.5 hours to obtain a reaction solution, then transferring the reaction solution to a high-pressure reactor, replacing the air in the reactor with an inert gas, and then stirring the reaction at 149°C under normal pressure for 4.5 hours, then reducing the pressure to 90 Pa, raising the temperature to 248°C, and maintaining the temperature and pressure while stirring the reaction for 23 hours, and finally cooling to room temperature after the reaction is completed. The polymer was precipitated in water, washed six times with ethanol, and finally dried at 93°C under vacuum to constant weight to obtain a rosin-based phenylphosphine oxide-based isoxazole-based functional polymer. The molar ratio of trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isooxazole dicarboxylic acid, catalyst, and high-boiling solvent was 1:0.5:0.5:1.1:9.5. The catalyst was a mixture of tetrabutyl titanate, p-toluenesulfonic acid, and antimony acetate in a mass ratio of 1:2:1. The high-boiling solvent was dimethyl sulfoxide. The inert gas was argon.

[0050] The acrylate rubber is ACM, brand AR74, a product of Zeon Corporation of Japan; the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber, brand T-55; the sound-absorbing material is sound-absorbing cotton; the sound-absorbing cotton has a density of 30 kg / m³. 3 Polyurethane foam.

[0051] A method for preparing the self-sealing quiet tire includes the following steps: Step S1: Perform high-energy laser cleaning on the inner wall surface of the tire body; Step S2: Add chlorohydrin rubber, acrylate rubber and rosin-based phenyl phosphine oxide isoxazole functional polymer to a two-roll mill for plasticizing and rolling. Then add other components of the self-healing adhesive layer and mix for 11 minutes. Next, add the rubber compound to solvent oil, stir evenly, and apply it to the inner wall surface of the tire body. Then attach the sound-absorbing material to the surface of the adhesive layer and cure at 158°C for 18 minutes.

[0052] The power of the high-energy laser cleaning in step S1 is 450 kW; the solvent oil in step S2 is No. 120 solvent oil; the mass ratio of the adhesive to the solvent oil is 2:1.

[0053] Example 5 A self-healing, quiet tire includes a tire body and a self-healing rubber layer and a noise-reducing material sequentially bonded to the inner wall of the tire body from the inside out. The self-healing rubber layer is composed of the following components in parts by weight: 30 parts of chlorohydrin rubber, 30 parts of acrylate rubber, 15 parts of rosin-based phenylphosphine oxide isoxazole functional polymer, 3 parts of 4,4-chloroformylphenyl ether, 2 parts of catalyst, 4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1.2 parts of trithiocyanate, 25 parts of filler, 0.6 parts of accelerator TMTD, and 3 parts of additives. The rosin-based phenylphosphine oxide isoxazole functional polymer comprises structural units introduced by the following monomers through a polycondensation reaction: trirosinyl glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, and 3,5-isooxazole dicarboxylic acid.

[0054] The additive is a mixture of an anti-aging agent, an environmentally friendly plasticizer, a softener, and an anti-scorching agent in a mass ratio of 1:2:1.2:0.5; the anti-aging agent is NBC; the environmentally friendly plasticizer is epoxidized soybean oil; the softener is naphthenic oil; and the anti-scorching agent is CTP.

[0055] The filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:12; the calcium carbonate has a particle size of 800 mesh; the magnesium oxide has a particle size of 1000 mesh; and the catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:5.

[0056] The preparation method of the rosin-based phenylphosphine oxide-isoxazole-based functional polymer includes the following steps: adding trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isoxazole dicarboxylic acid, and a catalyst to a high-boiling-point solvent, stirring at 130°C for 5 hours to obtain a reaction solution, then transferring the reaction solution to a high-pressure reactor, replacing the air in the reactor with an inert gas, and then stirring the reaction at 150°C under normal pressure for 5 hours, then reducing the pressure to 100 Pa, raising the temperature to 250°C, and maintaining the temperature and pressure while stirring for 24 hours. After the reaction was completed, the polymer was cooled to room temperature, precipitated in water, and then washed six times with ethanol. Finally, it was dried at 95°C under vacuum to constant weight to obtain a rosin-based phenylphosphine oxide-based isoxazole-based functional polymer. The molar ratio of trirosinate glycerol, bis(4-carboxyphenyl)phenylphosphine oxide, 3,5-isooxazole dicarboxylic acid, catalyst, and high-boiling solvent was 1:0.5:0.5:1.2:10. The catalyst was tetrabutyl titanate, the high-boiling solvent was dimethyl sulfoxide, and the inert gas was nitrogen.

[0057] The acrylate rubber is ACM, brand AR74, a product of Zeon Corporation of Japan; the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber, brand T-55; the sound-absorbing material is sound-absorbing cotton; the sound-absorbing cotton has a density of 30 kg / m³. 3 Polyurethane foam.

[0058] A method for preparing the self-sealing quiet tire includes the following steps: Step S1: Perform high-energy laser cleaning on the inner wall surface of the tire body; Step S2: Add chlorohydrin rubber, acrylate rubber and rosin-based phenylphosphine oxide isoxazole functional polymer to a two-roll mill for plasticizing and rolling. Then add other components of the self-healing adhesive layer and mix for 12 minutes. Next, add the rubber compound to solvent oil, stir evenly, and apply it to the inner wall surface of the tire body. Then attach the sound-absorbing material to the surface of the adhesive layer and cure at 160°C for 20 minutes.

[0059] The power of the high-energy laser cleaning in step S1 is 500 kW; the solvent oil in step S2 is No. 120 solvent oil; the mass ratio of the adhesive to the solvent oil is 2:1.

[0060] Comparative Example 1 A self-repairing silent tire and its preparation method are basically the same as in Example 1, except that 4,4-chloroformylphenyl ether is not added, and bis(4-carboxyphenyl)phenylphosphine oxide is used instead of 3,5-isoxazole dicarboxylic acid.

[0061] Comparative Example 2 A self-repairing silent tire and its preparation method are basically the same as in Example 1, except that 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane is not added, and 3,5-isoxazole dicarboxylic acid is used instead of bis(4-carboxyphenyl)phenylphosphine oxide.

[0062] To further illustrate the beneficial technical effects of the self-sealing quiet tires involved in the various embodiments of the present invention, relevant performance tests were conducted on the self-sealing quiet tires involved in Examples 1-5 and Comparative Examples 1-2. The thickness of the self-sealing adhesive layer was controlled at 3 mm, and the thickness of the polyurethane foam was 30 mm. The test results are shown in Table 1, and the test methods are as follows: (1) Self-healing performance: Take 5 tires of each example, for a total of 35 tires, inflate them with the same air pressure, and puncture them with iron nails with a diameter of 3mm. Then remove the iron nails and drive the tires at a speed of 70km / h for 150 minutes to test the change in tire air pressure. Remove the tested tires from the rim and observe and analyze the self-healing effect of the punctured parts with the naked eye. Whether healing has occurred is determined by observing the repair effect of the nail puncture after the test (○ indicates that at least one tire has not healed; ● indicates that all tires have healed). The repair effect is represented by "number of tires with constant tire pressure / number of tires with original normal tire pressure" for each example tire.

[0063] (2) Noise Reduction Effect: Using commercially available tires (model 205 / 55R16 91V) as the tire body, the tires manufactured in each example were installed on the same passenger car. The passenger car was driven at 80 km / h on a rough asphalt road. A microphone was installed in the driver's seat of the passenger car to monitor and record the noise from 20 to 10000 Hz. Based on the spectral characteristics of the tire cavity noise, the noise spectrum data of the 200-250 Hz frequency range was recorded, and the noise peak value in this frequency range was statistically analyzed.

[0064] Table 1 Test Project Whether healing occurs Repair effect noise peak unit - - dB Example 1 ● 5 / 5 32.23 Example 2 ● 5 / 5 32.01 Example 3 ● 5 / 5 31.65 Example 4 ● 5 / 5 31.45 Example 5 ● 5 / 5 31.22 Comparative Example 1 ○ 3 / 5 34.31 Comparative Example 2 ○ 4 / 5 33.59 As can be seen from the data in Table 1, the self-repairing quiet tires involved in the embodiments of the present invention have better self-repairing effect and superior quiet performance compared with the comparative products; the combined use of 4,4-chloroformylphenyl ether 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)phenylphosphine oxide and 3,5-isoxazole dicarboxylic acid is beneficial to improving the above performance.

[0065] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A self-repairing silent tire, characterized in that, The tire body and the self-repairing glue layer and the soundproof material sequentially attached to the inner wall of the tire body from inside to outside; the self-repairing glue layer comprises the following components by weight: chlorohydrin rubber 20-30 parts, acrylate rubber 20-30 parts, rosin-based phenyl phosphine oxide isoxazolyl functional polymer 10-15 parts, 4,4-chloroformyl phenyl ether 1-3 parts, catalyst 1-2 parts, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane 2-4 parts, thiocyanic acid 0.8-1.2 parts, filler 15-25 parts, accelerator TMTD 0.3-0.6 parts, and auxiliary agent 1-3 parts; the rosin-based phenyl phosphine oxide isoxazolyl functional polymer comprises the following monomers by condensation reaction: trimesyric acid glycerol ester, bis(4-carboxyphenyl)phenyl phosphine oxide, and 3,5-isoxazol dicarboxylic acid.

2. Self-repairing silent tyre according to claim 1, characterized in that, The auxiliary agent is a mixture of an anti-aging agent, an environmentally friendly plasticizer, a softening agent, and a scorch retarder in a mass ratio of 1:(1-2):(0.8-1.2):0.

5.

3. Self-repairing silent tyre according to claim 2, characterized in that, The anti-aging agent is anti-aging agent NBC; the environmentally friendly plasticizer is epoxy soybean oil; the softening agent is at least one of naphthenic oil and white oil; and the scorch retarder is scorch retarder CTP.

4. The self-repairing silent tire of claim 1, wherein, The filler is a mixture of calcium carbonate, magnesium oxide, and carbon black N550 in a mass ratio of 1:0.5:(8-12); the particle size of the calcium carbonate is 400-800 mesh; and the particle size of the magnesium oxide is 500-1000 mesh.

5. The self-repairing silent tire of claim 1, wherein, The catalyst is a mixture of anhydrous aluminum chloride and anhydrous ferric chloride in a mass ratio of 1:(3-5).

6. The self-repairing silent tire of claim 1, wherein, The preparation method of the rosin-based phenyl phosphine oxide isoxazolyl functional polymer comprises the following steps: adding trimesyric acid glycerol ester, bis(4-carboxyphenyl)phenyl phosphine oxide, 3,5-isoxazol dicarboxylic acid, and a catalyst into a high-boiling-point solvent, stirring at 110-130℃ for 3-5 hours to obtain a reaction solution, then transferring the reaction solution into a high-pressure reaction kettle, replacing the air in the kettle with an inert gas, then stirring at 145-150℃ under normal pressure for 3-5 hours, reducing the pressure to 50-100Pa, increasing the temperature to 240-250℃, stirring under pressure for 18-24 hours, cooling to room temperature after the reaction is completed, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying in a vacuum dryer at 85-95℃ until the weight is constant to obtain the rosin-based phenyl phosphine oxide isoxazolyl functional polymer.

7. Self-repairing silent tyre according to claim 6, characterized in that, The molar ratio of the trimesyric acid glycerol ester, bis(4-carboxyphenyl)phenyl phosphine oxide, 3,5-isoxazol dicarboxylic acid, catalyst, and high-boiling-point solvent is 1:0.5:0.5:(0.8-1.2):(6-10).

8. Self-repairing silent tire according to claim 6, characterized in that, The catalyst is at least one of titanium tetrabutoxide, p-toluenesulfonic acid, and antimony acetate; the high-boiling-point solvent is dimethyl sulfoxide; and the inert gas is any one of nitrogen, helium, neon, and argon.

9. The self-repairing silent tire of claim 1, wherein, The acrylic rubber is ACM with a brand AR74; the chlorohydrin rubber is a ternary copolymer chlorohydrin rubber with a brand T-55; the soundproof material is sound-absorbing cotton; the sound-absorbing cotton is polyurethane foam with a density of 20kg / m 3 -40kg / m 3 .

10. A process for the production of self-repairing silent tyres according to any one of claims 1-9, characterized in that, The method comprises the following steps: Step S1, high-energy laser cleaning is performed on the inner wall surface of the tire body; the power of the high-energy laser cleaning is 200-500kw; Step S2, chlorohydrin rubber, acrylate rubber and rosin-based phenyl phosphine oxide-based isoxazolyl functional polymer are added into a double-roller open mill for plasticizing and roll wrapping, and then other components of the self-repairing rubber layer are added for mixing for 8-12min, then the rubber compound is added into solvent oil, stirred uniformly, coated on the inner wall surface of the tire body, and then the noise-reducing material is attached on the surface of the rubber layer, and then cured at 150-160℃ for 10-20min; the solvent oil is No.120 solvent oil; the mass ratio of the rubber compound to the solvent oil is 2:1.