CN118755169B

CN118755169B - Tire, vulcanization method and application thereof

Info

Publication number: CN118755169B
Application number: CN202411237042.7A
Authority: CN
Inventors: 邱文通; 邱小铭; 邱昱华
Original assignee: Shandong Zhentai Group Co ltd
Current assignee: Shandong Zhentai Group Co ltd
Priority date: 2024-09-05
Filing date: 2024-09-05
Publication date: 2024-11-08
Anticipated expiration: 2044-09-05
Also published as: CN118755169A

Abstract

The invention relates to the technical field of tires, and provides a tire, a vulcanization method and application thereof, wherein the tire comprises a tire body and a tread, and tread rubber of the tread comprises the following raw materials in parts by weight: 90-120 parts of styrene-butadiene rubber, 20-30 parts of eucommia ulmoides rubber, 30-40 parts of white carbon black, 5-8 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator, 1-2 parts of zinc oxide, 10-15 parts of phenyl POSS grafted polyethylene polyamine, 8-10 parts of carbon nano tube and 5-8 parts of chlorinated paraffin. The rigidity and nano-scale reinforcement provided by the phenyl POSS in the tread rubber in grafting with the phenyl POSS in the polyethylene polyamine, the plasticity and toughness of the polyethylene polyamine and the lubricity of the chlorinated paraffin are mutually complemented, so that obvious synergistic effect is generated in the aspects of improving the wear resistance and the crack resistance of the material. This synergistic mechanism not only improves the overall performance of the tire, but also enhances its reliability and durability in a variety of use environments.

Description

Tire, vulcanization method and application thereof

Technical Field

The invention relates to the technical field of tires, in particular to a tire, a vulcanization method and application thereof.

Background

The oblique agricultural tire is of great importance in the field of agricultural machinery, and is widely applied to equipment such as tractors, harvesters and the like because of being suitable for diversified working environments and firm structural design. The bias tire is characterized by a multi-layer crossed angle overlapped ply structure, and the structure not only enhances the strength and durability of the tire, but also improves the resistance to side impact, so that the bias tire has excellent steering performance on uneven terrain in the field. However, as modern agriculture has increased in demand for efficient and sustainable development, further optimization of the performance of these tires has become an important research direction.

Tread band is an important component of bias agricultural tires because it directly affects the grip, wear resistance, and service life of the tire. The traditional tread rubber is mainly prepared from a combination of natural rubber and synthetic rubber, and reinforcing materials such as carbon black and the like are added to improve the wear resistance and ageing resistance of the tread rubber. While this combination effectively improves the basic performance of the tire, its durability and crack resistance remain to be improved under long-term heavy-duty and high-wear conditions. In addition, tires may be damaged by sharp objects such as stones and root burrs during field operations, and thus improvement of the cutting resistance of tread rubber is also an indispensable field of improvement.

To address these technical challenges, current research efforts have focused on exploring new materials and applications for modified fillers. The invention patent number CN109593242A discloses a tread rubber material of an oblique crossing heavy truck tire, and the increase of the styrene content can improve the elastic modulus and the tear resistance, but too high styrene can cause the increase of plasticity, thereby affecting the wear resistance and the overall durability. Therefore, the development of more durable and efficient bias agricultural tires is needed, the production efficiency and the operation reliability of agricultural machinery are effectively improved, and the requirements of modern agriculture on high-performance tires are met.

Disclosure of Invention

In view of the above, the invention provides a tire, a vulcanization method and application thereof, which are used for solving the technical problems of poor wear resistance and crack resistance of the tread rubber of the conventional bias agricultural tire and prolonging the service life of the tire.

The technical scheme of the invention is realized as follows: the invention provides a tire, which comprises a tire body and a tire tread, wherein the tire tread rubber of the tire tread comprises the following raw materials in parts by weight: 90-120 parts of styrene-butadiene rubber, 20-30 parts of eucommia ulmoides rubber, 30-40 parts of white carbon black, 5-8 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator, 1-2 parts of zinc oxide, 10-15 parts of phenyl POSS grafted polyethylene polyamine, 8-10 parts of carbon nano tube and 5-8 parts of chlorinated paraffin.

The eucommia ulmoides rubber has the characteristic of rubber and plastic dual property, can effectively improve the wear resistance of the tread and prolong the service life of the tire. The styrene-butadiene rubber provides good elasticity and flexibility, and can better adapt to the impact and vibration of the tire on uneven ground after being combined with the eucommia ulmoides rubber, so that the running stability is improved.

The nanoscale structure of the phenyl POSS forms an optimized network with polyethylene polyamine through crosslinking, so that the whole material bears larger stress in the friction process and is not easy to wear. In addition, the crosslinking between the phenyl POSS and the polyethylene polyamine enhances stress dispersion, and the flexibility of the polyethylene polyamine allows the material to deform more under stress, thereby delaying crack formation and inhibiting crack propagation. Meanwhile, the combination of the phenyl POSS and the polyethylene polyamine enables the molecular structure of the material to be more orderly, the deformation during rolling is smoother, and the friction force required to be overcome during rolling is reduced.

The lubricating effect brought by the chlorinated paraffin obviously reduces the internal friction and dynamic viscosity of the material, so that the molecular chain can flow more smoothly under load, and the energy loss caused by friction is reduced. In addition, chlorinated paraffin as a plasticizer improves the ductility of the material and reduces its brittleness.

The phenyl POSS grafted polyethylene polyamine and the chlorinated paraffin are mutually complemented, so that remarkable synergistic effects are generated in the aspects of improving the wear resistance and the crack resistance of the material and reducing the rolling resistance. This synergistic mechanism not only improves the overall performance of the tire, but also enhances its reliability and durability in a variety of use environments.

In addition, the organic-inorganic mixing characteristic of POSS makes it have good interface compatibility with rubber, white carbon black and carbon nanotube, thus promote the uniform dispersion of the reinforcing material, raise the overall strength and wearability of the composite material.

When zinc oxide is used as an important active agent in a vulcanization system and is used together with chlorinated paraffin, the network crosslinking efficiency in the vulcanization process is enhanced, and the heat resistance and the strength of rubber are improved.

On the basis of the technical scheme, preferably, the preparation method of the phenyl POSS grafted polyethylene polyamine comprises the following steps of:

S1, dissolving phenyl POSS in anhydrous dichloromethane to obtain phenyl POSS solution, and dissolving polyethylene polyamine in absolute ethyl alcohol to obtain polyethylene polyamine solution;

S2, mixing the phenyl POSS solution and the polyethylene polyamine solution, adding triethylamine, stirring at 20-30 ℃ for reaction for 0.5-1h, then heating to 50-70 ℃, continuing to react for 3-4h, and cooling, drying and rotary steaming after the reaction is finished to remove the solvent to obtain the phenyl POSS grafted polyethylene polyamine.

Based on the above technical scheme, preferably, in step S2, chlorinated (1-butyl-3-methylimidazole) is added into the phenyl POSS solution, and the mixture is mixed with the polyethylene polyamine solution after being stirred uniformly.

Specifically, the ionic liquid enhances the interaction between POSS and polyethylene polyamine in the reaction process, so that a crosslinked network is more uniform and stable, and meanwhile, the dispersion and interaction of other components are improved in the mixing process, and particularly the dispersibility of the inorganic reinforcing material is improved, so that the strength of the material can be improved. In addition, by improving the fluidity of the molecular chain, the ionic liquid can effectively disperse stress, reduce the formation of microcracks and enhance the crack resistance. The ionic liquid reduces internal friction and enhances the dynamic response of the material by optimizing the movement state of a molecular chain, thereby effectively reducing rolling resistance.

On the basis of the technical scheme, preferably, the mass ratio of the phenyl POSS to the polyethylene polyamine to the triethylamine is 1:1.5-2.5:0.05-0.15, the mass ratio of the phenyl POSS to the anhydrous dichloromethane is 1:10-50, the mass ratio of the polyethylene polyamine to the anhydrous ethanol is 1:5-10, and the mass ratio of the chlorinated (1-butyl-3-methylimidazole) to the phenyl POSS is 0.1-1:1.

On the basis of the technical scheme, preferably, the chlorinated paraffin is pretreated by the following treatment method: and (3) performing arc plasma treatment on the chlorinated paraffin for 5-10min under the direct-current voltage of 30-50kV to obtain the activated chlorinated paraffin.

Specifically, the arc plasma pretreatment increases the surface activity of chlorinated paraffin, thereby enhancing its bonding with natural rubber and butyl rubber. After the chlorinated paraffin is treated, the chlorinated paraffin can be synergistic with stearic acid, so that the interface bonding and crosslinking stability are improved, the overall strength and toughness of the material are enhanced, and the propagation and expansion of cracks are further reduced.

In addition, the pretreated chlorinated paraffin is easier to disperse in the colloid, so that the lubricity of the material is enhanced, and the internal friction and energy loss can be effectively reduced, thereby reducing the rolling resistance.

On the basis of the technical scheme, preferably, the phenyl POSS is one or two of POSS-phenyl and octa-para-aminophenyl-POSS; the vulcanizing agent is sulfur or phenolic resin, and the vulcanizing accelerator is one or more of N-cyclohexyl-2-benzothiazole sulfenamide, N' -diphenyl-thiourea and 2-mercaptobenzothiazole.

On the other hand, the invention also provides a tire vulcanizing method, which is characterized in that: the method comprises the following steps:

S1, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, adding carbon nano tubes and quercetin for secondary mixing, continuously adding chlorinated paraffin, vulcanizing agent and vulcanization accelerator for tertiary mixing, and tabletting after mixing is finished to obtain a mixed film;

S2, bonding the rubber sheet on the outer side of the tire body, placing the rubber sheet in a mold, and vulcanizing for 50-80 min at 138-148 ℃ to obtain the tire.

Specifically, quercetin can be used as an antioxidant in the compound to delay adverse side reactions in the vulcanization process, and can also cooperate with a vulcanizing agent and a vulcanization accelerator to optimize the structure of a vulcanization network and promote more uniform crosslinking, so that the fatigue resistance of tread rubber is enhanced. In addition, the microstructure formed by the quercetin in the material is beneficial to enhancing the formation of crystals and improving the wear resistance of the tread rubber. The antioxidant properties of quercetin also reduce heat caused by friction, thereby reducing friction enhancement and rolling resistance increase due to aging.

On the basis of the technical scheme, preferably, the mass ratio of the quercetin to the carbon nano tube is 0.5-1:8-10.

Based on the technical proposal, the temperature of primary mixing is preferably 60-80 ℃ and the time is 3-5min; the temperature of the secondary mixing is 100-120 ℃ and the time is 6-8min; the temperature of the three mixing is 130-150 ℃ and the time is 5-10min.

In still another aspect, the invention further provides an application of the tire tread rubber in preparing an oblique agriculture tire.

Compared with the prior art, the tire and the vulcanization method and application thereof have the following beneficial effects:

(1) The phenyl POSS has good dispersibility and compatibility with organic polymers. The phenyl POSS grafted polyethylene polyamine can increase the wear resistance and crack resistance of the tread rubber by enhancing the interaction force of molecular chains. In addition, the chlorinated paraffin is used as a plasticizer and a protective agent, so that the flexibility and weather resistance of the rubber material can be improved, and the resistance of the tread rubber to physical damage and the service life of the tread rubber are improved. The combined action of the two components makes the molecular structure of the sizing material more compact, effectively reduces the development of abrasion and cracks, and simultaneously slightly reduces the internal consumption of the material, thereby reducing the rolling resistance.

(2) The introduction of the (1-butyl-3-methylimidazole) chloride ionic liquid is helpful for improving the interfacial compatibility of the phenyl POSS and polyethylene polyamine, and promoting the reaction to proceed, so as to form stable chemical bonds. This stability enhances the crosslink density of the rubber material, increasing the strength and wear resistance of the tread band.

(3) The chlorinated paraffin is activated by arc plasma, so that active groups can be introduced, and the adhesiveness between the chlorinated paraffin and a rubber matrix is improved. The activation treatment enhances the cross-linking structure in the material, improves the overall mechanical strength of the sizing material, and improves the wear resistance. The stronger cross-linked network also means that there is greater resistance to crack propagation, thereby enhancing the crack resistance of the tread band. Meanwhile, the high-efficiency chemical bond combination ensures that the internal structure of the material is more compact, reduces the energy loss caused by friction, and is also beneficial to reducing the rolling resistance.

(4) Quercetin is a natural antioxidant and free radical scavenger, and the introduction of the quercetin helps to improve the ageing resistance of rubber. This not only improves the durability of the tread rubber, but also enhances crack resistance by reducing the formation of crack sources by inhibiting the oxidative degradation process. At the same time, its own biocompatibility and reinforcement contribute to further optimizing the physical properties of the tread and reducing the rolling resistance.

Detailed Description

The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.

Eucommia ulmoides rubber (synthetic 1, 4-trans polyisoprene rubber) used in the invention is purchased from Wuhan Yuan Co-creation technology Co., ltd; styrene butadiene rubber, model NS612, ZEON chemical company limited; white carbon black, model 200MP, soy chemical products.

In the examples and comparative examples of the present invention, 1 part by weight was 100g.

Example 1

The tread rubber of the embodiment comprises the following raw materials in parts by weight: 110 parts of styrene-butadiene rubber, 26 parts of eucommia rubber, 35 parts of white carbon black, 7 parts of sulfur, 2 parts of N-cyclohexyl-2-benzothiazole sulfenamide, 1.5 parts of zinc oxide, 13 parts of phenyl POSS grafted polyethylene polyamine, 9 parts of carbon nano tube and 7 parts of chlorinated paraffin.

The preparation method of the phenyl POSS grafted polyethylene polyamine comprises the following steps:

S1, dissolving 10g of octa-para-aminophenyl-POSS in 300g of anhydrous dichloromethane to obtain octa-para-aminophenyl-POSS solution, and dissolving 20g of polyethylene polyamine in 120g of absolute ethanol to obtain polyethylene polyamine solution;

S2, mixing the octa-para-aminophenyl-POSS solution prepared in the step S1 with a polyethylene polyamine solution, adding 1g of triethylamine, stirring at 30 ℃ for reaction for 1h, then heating to 50 ℃, continuing to react for 3h, and cooling, drying and rotary steaming after the reaction is finished to remove the solvent to obtain the phenyl POSS grafted polyethylene polyamine.

The tread rubber mixing method comprises the following steps: mixing styrene butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine for 5min at 75 ℃; adding carbon nano tubes for secondary mixing, wherein the mixing temperature is 110 ℃ and the mixing time is 8min; and (3) continuously adding chlorinated paraffin, sulfur and N-cyclohexyl-2-benzothiazole sulfenamide for three times of mixing, wherein the mixing temperature is 135 ℃, the mixing time is 10min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Example 2

The difference between this embodiment and embodiment 1 is that: when phenyl POSS grafted polyethylene polyamine is prepared, chloridized (1-butyl-3-methylimidazole) ionic liquid is added, and the rest contents are the same.

Specifically, the preparation method of the phenyl POSS grafted polyethylene polyamine comprises the following steps:

S2, adding 5g of chloridized (1-butyl-3-methylimidazole) into the octa-para-aminophenyl-POSS solution prepared in the step S1, uniformly stirring, mixing with a polyethylene polyamine solution, adding 1g of triethylamine, stirring at 30 ℃ for reaction for 1h, heating to 50 ℃, continuing to react for 3h, and cooling, drying and removing solvent by rotary evaporation after the reaction is finished to obtain the phenyl POSS grafted polyethylene polyamine.

Example 3

The difference between this embodiment and embodiment 2 is that: the chlorinated paraffin is pretreated and then mixed, and the rest content is the same.

Specifically, the tread rubber mixing method comprises the following steps:

s1, pretreatment of chlorinated paraffin: the chlorinated paraffin was arc plasma treated at a direct current voltage of 40kV for 8min to obtain an activated chlorinated paraffin.

S2, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, wherein the mixing temperature is 75 ℃ and the mixing time is 5min; adding carbon nano tubes for secondary mixing, wherein the mixing temperature is 110 ℃ and the mixing time is 8min; continuously adding activated chlorinated paraffin, sulfur and N-cyclohexyl-2-benzothiazole sulfenamide for three times of mixing, wherein the mixing temperature is 135 ℃, the time is 10min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Example 4

The difference between this embodiment and embodiment 3 is that: during secondary mixing, quercetin was added, and the rest was the same.

Specifically, the tread rubber mixing method comprises the following steps:

S2, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, wherein the mixing temperature is 75 ℃ and the mixing time is 5min; adding 0.8 part of carbon nano tube to carry out secondary mixing, wherein the mixing temperature is 110 ℃ and the mixing time is 8min; continuously adding activated chlorinated paraffin, sulfur and N-cyclohexyl-2-benzothiazole sulfenamide for three times of mixing, wherein the mixing temperature is 135 ℃, the time is 10min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Example 5

The tread rubber of the embodiment comprises the following raw materials in parts by weight: 90 parts of styrene-butadiene rubber, 22 parts of eucommia ulmoides rubber, 30 parts of white carbon black, 6 parts of phenolic resin, 1 part of N, N' -diphenyl-thiourea, 1.3 parts of zinc oxide, 10 parts of phenyl POSS grafted polyethylene polyamine, 8 parts of carbon nano tubes and 8 parts of chlorinated paraffin.

s1, dissolving 10g of phenyl POSS in 100g of anhydrous dichloromethane to obtain phenyl POSS solution, and dissolving 25g of polyethylene polyamine in 125g of absolute ethyl alcohol to obtain polyethylene polyamine solution;

S2, adding 8g of (1-butyl-3-methylimidazole) chloride into the phenyl POSS solution prepared in the step S1, uniformly stirring, mixing with the polyethylene polyamine solution, adding 0.5g of triethylamine, stirring at 20 ℃ for reaction for 0.5h, heating to 70 ℃, continuing to react for 4h, and cooling, drying and steaming to remove the solvent after the reaction is finished to obtain the phenyl POSS grafted polyethylene polyamine.

The tread rubber mixing method comprises the following steps:

S1, pretreatment of chlorinated paraffin: the chlorinated paraffin was arc plasma treated at a direct current voltage of 30kV for 8min to obtain an activated chlorinated paraffin.

S2, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, wherein the mixing temperature is 60 ℃ and the mixing time is 5min; adding 1 part of carbon nano tube and quercetin for secondary mixing, wherein the mixing temperature is 100 ℃ and the mixing time is 7min; and continuously adding activated chlorinated paraffin, phenolic resin and N, N' -diphenyl-thiourea for three times of mixing, wherein the mixing temperature is 130 ℃, the mixing time is 8min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Example 6

The tread rubber of the embodiment comprises the following raw materials in parts by weight: 100 parts of styrene-butadiene rubber, 30 parts of eucommia ulmoides rubber, 33 parts of white carbon black, 5 parts of sulfur, 1.5 parts of 2-mercaptobenzothiazole, 1 part of zinc oxide, 11 parts of phenyl POSS grafted polyethylene polyamine, 10 parts of carbon nano tube and 6 parts of chlorinated paraffin.

S1, dissolving 10g of phenyl POSS in 500g of anhydrous dichloromethane to obtain phenyl POSS solution, and dissolving 18g of polyethylene polyamine in 150g of absolute ethanol to obtain polyethylene polyamine solution;

S2, adding 1g of (1-butyl-3-methylimidazole) chloride into the phenyl POSS solution prepared in the step S1, uniformly stirring, mixing with the polyethylene polyamine solution, adding 1.5g of triethylamine, stirring at 25 ℃ for reaction for 1h, heating to 55 ℃, continuing to react for 3.5h, and cooling, drying and steaming to remove the solvent after the reaction is finished to obtain the phenyl POSS grafted polyethylene polyamine.

The tread rubber mixing method comprises the following steps:

s1, pretreatment of chlorinated paraffin: the chlorinated paraffin was arc plasma treated at a direct current voltage of 50kV for 8min to obtain an activated chlorinated paraffin.

S2, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, wherein the mixing temperature is 80 ℃ and the mixing time is 3min; adding 0.7 part of carbon nano tube and quercetin for secondary mixing, wherein the mixing temperature is 120 ℃ and the mixing time is 6min; continuously adding activated chlorinated paraffin, sulfur and 2-mercaptobenzothiazole to carry out three times of mixing, wherein the mixing temperature is 150 ℃, the time is 5min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Example 7

The tread rubber of the embodiment comprises the following raw materials in parts by weight: 120 parts of styrene-butadiene rubber, 28 parts of eucommia ulmoides rubber, 40 parts of white carbon black, 7 parts of sulfur, 3 parts of N-cyclohexyl-2-benzothiazole sulfenamide, 1.6 parts of zinc oxide, 15 parts of phenyl POSS grafted polyethylene polyamine, 9 parts of carbon nano tube and 5 parts of chlorinated paraffin.

S1, dissolving 10g of phenyl POSS in 400g of anhydrous dichloromethane to obtain phenyl POSS solution, and dissolving 25g of polyethylene polyamine in 200g of absolute ethanol to obtain polyethylene polyamine solution;

S2, adding 10g of (1-butyl-3-methylimidazole) chloride into the phenyl POSS solution prepared in the step S1, uniformly stirring, mixing with the polyethylene polyamine solution, adding 1g of triethylamine, stirring at 30 ℃ for reaction for 0.5h, heating to 65 ℃, continuing to react for 4h, and cooling, drying and steaming to remove the solvent after the reaction is finished to obtain the phenyl POSS grafted polyethylene polyamine.

The tread rubber mixing method comprises the following steps:

S1, pretreatment of chlorinated paraffin: the chlorinated paraffin was arc plasma treated at a direct current voltage of 35kV for 8min to obtain an activated chlorinated paraffin.

S2, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, wherein the mixing temperature is 75 ℃ and the mixing time is 5min; adding 0.9 part of carbon nano tube and quercetin for secondary mixing, wherein the mixing temperature is 120 ℃ and the mixing time is 8min; continuously adding activated chlorinated paraffin, sulfur and N-cyclohexyl-2-benzothiazole sulfenamide for three times of mixing, wherein the mixing temperature is 145 ℃, the mixing time is 10min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Example 8

The tread rubber of the embodiment comprises the following raw materials in parts by weight: 115 parts of styrene-butadiene rubber, 20 parts of eucommia ulmoides rubber, 38 parts of white carbon black, 8 parts of phenolic resin, 2.5 parts of N, N' -diphenyl-thiourea, 2 parts of zinc oxide, 14 parts of phenyl POSS grafted polyethylene polyamine, 8.5 parts of carbon nano tubes and 7.5 parts of chlorinated paraffin.

S1, dissolving 10g of phenyl POSS in 200g of anhydrous dichloromethane to obtain phenyl POSS solution, and dissolving 22g of polyethylene polyamine in 150g of absolute ethyl alcohol to obtain polyethylene polyamine solution;

s2, adding 3g of (1-butyl-3-methylimidazole) chloride into the phenyl POSS solution prepared in the step S1, uniformly stirring, mixing with the polyethylene polyamine solution, adding 1g of triethylamine, stirring at 30 ℃ for reaction for 1h, heating to 60 ℃, continuing to react for 3h, and cooling, drying and steaming to remove the solvent to obtain the phenyl POSS grafted polyethylene polyamine.

The tread rubber mixing method comprises the following steps:

S1, pretreatment of chlorinated paraffin: the chlorinated paraffin was arc plasma treated at a direct current voltage of 45kV for 8min to obtain an activated chlorinated paraffin.

S2, performing primary mixing on styrene-butadiene rubber, eucommia ulmoides rubber, white carbon black, zinc oxide and phenyl POSS grafted polyethylene polyamine, wherein the mixing temperature is 65 ℃ and the mixing time is 5min; adding 0.5 part of carbon nano tube and quercetin for secondary mixing, wherein the mixing temperature is 115 ℃ and the mixing time is 8min; and continuously adding activated chlorinated paraffin, phenolic resin and N, N' -diphenyl-thiourea for three times of mixing, wherein the mixing temperature is 145 ℃, the mixing time is 10min, and tabletting is carried out after the mixing is finished to obtain a mixed film.

Comparative example 1

Comparative example 1 was compared to example 1, except that the phenyl POSS was absent to graft polyethylene polyamine.

Comparative example 2

Comparative example 2 was identical to example 1 in the absence of chlorinated paraffin.

Comparative example 3

Comparative example 3 the phenyl POSS graft polyethylene polyamine was out of the limit, specifically 30 parts, with the remainder being the same as in example 1.

Comparative example 4

Comparative example 4 compared with example 1, chlorinated paraffin was out of the limit, specifically 15 parts, and the rest was the same.

Comparative example 5

Comparative example 5 compared with example 1, the eucommia ulmoides rubber was out of the limit, specifically 40 parts, and the rest was the same.

The tread bands prepared in the above examples and comparative examples were tested for their properties, wherein the abrasion resistance test was referred to GB/T1689-2014, the rolling resistance was characterized by an index of Tan delta at 60℃and the strength was tested, and the results are given in the following Table.

Table 1 tread band performance

The cut resistance index indicates the cut resistance of the tread rubber, and the higher the value is, the better the cut resistance is, and the better the puncture resistance is. DIN abrasion index indicates the abrasion resistance of the tread band, with higher values indicating better abrasion resistance. The lower the rolling resistance is at 60 ℃ the lower the Tan delta value is, the lower the rolling resistance is of the surface tread rubber,

As shown in Table 1, the tread rubber of the examples of the present invention has stronger abrasion resistance and strength than those of the comparative examples, and it can be derived from comparative examples 1 to 2 and examples 1 to 4: (1) After the phenyl POSS is added to branch polyethylene polyamine and chlorinated paraffin, the interaction force of a colloid molecular chain is enhanced, so that the intermolecular structure of the sizing material is more compact, the development of abrasion and cracks is effectively reduced, and meanwhile, the rolling resistance is also reduced. (2) The ionic liquid enhances the interaction between the phenyl POSS and the polyethylene polyamine, so that a crosslinked network is more stable, and the overall performance of the colloid is improved. (3) After the chlorinated paraffin is activated, more active groups are introduced, so that the crosslinking strength of each component is enhanced, the overall strength and wear resistance are improved, meanwhile, the energy loss generated by friction is reduced, and the rolling resistance is reduced. (4) The increase of the quercetin promotes the vulcanization, optimizes the vulcanization network structure, enhances the tearing resistance and the cutting resistance of the tread rubber, and simultaneously has the oxidation resistance of the quercetin to enhance the friction and the rolling resistance caused by aging.

Comparative examples 3 to 5 can be given as follows: the excessive use of phenyl POSS grafted polyethylene polyamines increases the hardness and brittleness of the material, which in turn results in reduced tear strength. In addition, excess phenyl POSS grafted polyethylene polyamines may result in excessive crosslinking, degrading the elasticity of the rubber, reducing wear resistance and cut resistance. Excessive chlorinated paraffin can excessively soften rubber, reduce mechanical strength and wear resistance, and increase abrasion. Too much amount of eucommia ulmoides rubber affects the uniformity of the material, thereby causing deterioration of tear resistance, rolling resistance and cutting resistance.

In view of the strong cutting resistance and wear resistance and low rolling resistance of the tread rubber, the tread rubber can be used for the tread rubber of the diagonal agricultural tire.

When the oblique agricultural tire is prepared, the mixed rubber sheet is adhered to the outer side of the tire body, and is placed in a die to be vulcanized for 50-80 min at 138-148 ℃ to obtain the oblique agricultural tire.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims

1. A tire, characterized in that: the tire tread rubber comprises a tire body and a tire tread, and the tire tread rubber comprises the following raw materials in parts by weight: 90-120 parts of styrene-butadiene rubber, 20-30 parts of eucommia ulmoides rubber, 30-40 parts of white carbon black, 5-8 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator, 1-2 parts of zinc oxide, 10-15 parts of phenyl POSS grafted polyethylene polyamine, 8-10 parts of carbon nano tube and 5-8 parts of chlorinated paraffin;

The chlorinated paraffin is pretreated by the following treatment method: and (3) performing arc plasma treatment on the chlorinated paraffin for 5-10min under the direct-current voltage of 30-50kV to obtain the activated chlorinated paraffin.

2. A tyre as claimed in claim 1, wherein: the preparation method of the phenyl POSS grafted polyethylene polyamine comprises the following steps:

S2, mixing a phenyl POSS solution and a polyethylene polyamine solution, adding triethylamine, stirring at 20-30 ℃ for reaction for 0.5-1h, then heating to 50-70 ℃, continuing to react for 3-4h, and cooling, drying and rotary steaming after the reaction is finished to remove a solvent to obtain phenyl POSS grafted polyethylene polyamine;

The phenyl POSS is one or two of POSS-phenyl and octa-para-aminophenyl-POSS;

In the step S2, adding chlorinated (1-butyl-3-methylimidazole) into the phenyl POSS solution, uniformly stirring, and mixing with the polyethylene polyamine solution.

3. A tyre as claimed in claim 2, wherein: the mass ratio of the phenyl POSS to the polyethylene polyamine to the triethylamine is 1:1.5-2.5:0.05-0.15, the mass ratio of the phenyl POSS to the anhydrous dichloromethane is 1:10-50, the mass ratio of the polyethylene polyamine to the anhydrous ethanol is 1:5-10, and the mass ratio of the chlorinated (1-butyl-3-methylimidazole) to the phenyl POSS is 0.1-1:1.

4. A tyre as claimed in claim 1, wherein: the vulcanizing agent is sulfur or phenolic resin, and the vulcanizing accelerator is one or more of N-cyclohexyl-2-benzothiazole sulfenamide, N' -diphenyl-thiourea and 2-mercaptobenzothiazole.

5. A method of vulcanisation of a tyre according to any of the claims from 1 to 4, characterized in that: the method comprises the following steps:

6. A method of curing a tire as in claim 5, wherein: the mass ratio of the quercetin to the carbon nano tube is 0.5-1:8-10.

7. A method of curing a tire as in claim 5, wherein: the temperature of the primary mixing is 60-80 ℃ and the time is 3-5min; the temperature of the secondary mixing is 100-120 ℃ and the time is 6-8min; the temperature of the three mixing is 130-150 ℃ and the time is 5-10min.

8. Use of a tread band of a tyre according to any one of claims 1 to 4 for the preparation of a bias agriculture tyre.