Graphene reinforced aircraft tire inner liner rubber and preparation method thereof

Abstract

The invention belongs to the technical field of aircraft tires, and particularly relates to graphene-reinforced inner liner rubber for an aircraft tire and a preparation method of the graphene-reinforced inner liner rubber. The graphene reinforced aircraft tire inner liner rubber provided by the invention is prepared from 60 to 80 parts of halogenated butyl rubber, 10 to 30 parts of natural rubber, 10 to 20 parts of butadiene styrene rubber, 10 to 40 parts of N326 carbon black, 20 to 50 parts of semi-reinforced carbon black, 3 to 5 parts of dibutyl phthalate, 0.5 to 2 parts of stearic acid, 3 to 5 parts of zinc oxide, 0 to 1 part of magnesium oxide, 1 to 3 parts of tackifying resin, 1 to 2 parts of homogenizing agent, 1.5 to 2 parts of anti-aging agent, 0.5 to 2 parts of accelerant, 1 to 2 parts of insoluble sulfur and 0 to 0.5 part of scorch retarder. The invention designs the formula of the inner liner rubber for the aircraft tire, which is excellent in air tightness, good in mechanical property and excellent in aging resistance, and the inner liner rubber can maintain the stability of the internal air pressure of the aircraft tire for a long time and can effectively ensure the use safety of the aircraft tire.

Description

Technical Field

[0001] The invention belongs to the technical field of aircraft tires, and in particular relates to an airtight layer adhesive for graphene-reinforced aircraft tires and a preparation method thereof. Background Art

[0002] At present, most of the aviation tires at home and abroad are tubeless tires. By setting an airtight layer with good air permeability in the innermost layer of the tire, it can prevent internal gas leakage and protect the tire carcass cord layer.

[0003] During the use of aircraft tires, the airtight layer has high temperature and high frequency deformation. The harsh service conditions require that the airtight layer glue must ensure excellent airtightness to ensure the safety of aircraft takeoff and landing. The existing airtight layer glue of aircraft tires has the problem of insufficient airtightness. Summary of the invention

[0004] The purpose of the present invention is to provide a graphene-reinforced airtight layer rubber for aircraft tires and a preparation method thereof. The present invention realizes uniform dispersion of two-dimensional layered nano-graphene fillers in a rubber matrix through a graphene masterbatch, and designs an airtight layer rubber formula for aircraft tires with excellent air tightness, good mechanical properties, and excellent aging resistance. The airtight layer rubber can maintain the stability of the internal air pressure of the aircraft tire for a long time, and can effectively ensure the safety of the aircraft tire.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a graphene-reinforced airtight layer adhesive for aviation tires, comprising the following raw materials in parts by weight:

[0007] 60-80 parts of halogenated butyl rubber, 10-30 parts of natural rubber, 10-20 parts of styrene-butadiene rubber, 10-40 parts of N326 carbon black, 20-50 parts of semi-reinforcing carbon black, 3-5 parts of dibutyl phthalate, 0.5-2 parts of stearic acid, 3-5 parts of zinc oxide, 0-1 part of magnesium oxide, 1-3 parts of tackifying resin, 1-2 parts of leveling agent, 1.5-2 parts of antioxidant, 0.5-2 parts of accelerator, 1-2 parts of insoluble sulfur, 0-0.5 parts of scorch retarder;

[0008] The natural rubber is graphene masterbatch, or graphene masterbatch and smoked sheet rubber.

[0009] Preferably, the halogenated butyl rubber includes brominated butyl rubber and / or chlorinated butyl rubber.

[0010] Preferably, the tackifying resin is SP1068;

[0011] The homogenizer is 40MSF;

[0012] The antioxidant is a p-phenylenediamine antioxidant;

[0013] The accelerator includes one or more of thiazole accelerators, sulfenamide accelerators and thiuram accelerators;

[0014] The insoluble sulfur is IS-60;

[0015] The anti-scorching agent is anti-scorching agent CTP.

[0016] Preferably, the p-phenylenediamine antioxidant includes antioxidant 4010NA and / or antioxidant 4020.

[0017] Preferably, the thiazole accelerator includes accelerator DM and / or accelerator M;

[0018] The sulfenamide accelerator includes one or more of accelerator NOBS, accelerator DZ and accelerator CZ;

[0019] The thiuram accelerator includes one or more of accelerator TETD, accelerator TMTD and accelerator TBTD.

[0020] Preferably, the following mass parts of raw materials are included:

[0021] 70 parts of chlorinated butyl rubber, 20 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur, and 0.3 parts of scorch retarder CTP.

[0022] Preferably, the following mass parts of raw materials are included:

[0023] 80 parts of brominated butyl rubber, 10 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 30 parts of N326 carbon black, 30 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of magnesium oxide, 2 parts of tackifying resin SP1068, 1.5 parts of leveling agent 40MSF, 2 parts of antioxidant 4020, 0.5 parts of accelerator TMTD, 1 part of accelerator DM, and 0.6 parts of insoluble sulfur.

[0024] The present invention provides a method for preparing the graphene-reinforced airtight layer adhesive for aircraft tires described in the above technical solution, comprising the following steps:

[0025] Step 1, putting halogenated butyl rubber, natural rubber, styrene-butadiene rubber, a homogenizer and a tackifying resin into an internal mixer according to a certain proportion, and mixing and kneading;

[0026] Step 2, adding the antioxidant and stearic acid into the internal mixer according to the proportion, and mixing and kneading;

[0027] Step 3, adding N326 carbon black, semi-reinforcing carbon black and dibutyl phthalate into the internal mixer described in step 1 according to a certain proportion, and mixing and kneading;

[0028] Step 4, discharging the mixture obtained in step 3 from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber;

[0029] Step 5, after the first rubber mix is ​​placed aside, insoluble sulfur, magnesium oxide, zinc oxide, accelerator and scorch retarder are put into an internal mixer according to a proportion with the first rubber mix, and mixed and kneaded;

[0030] Step six, discharge the mixture obtained in step five from the internal mixer to a tablet press, cool it, and place it aside to obtain a graphene-enhanced airtight layer compound for aircraft tires.

[0031] Preferably, the mixing and kneading temperature in step 1 is raised to 110° C.

[0032] In step 2, the mixing and kneading temperature is increased from 110°C to 120°C;

[0033] In step 3, the mixing and kneading temperature is increased from 120°C to 140°C.

[0034] Preferably, the parking time is 16 to 24 hours;

[0035] In step 5, the mixing and kneading temperature is increased to 100°C.

[0036] The invention provides a graphene-reinforced airtight layer rubber for an aircraft tire. The airtight layer rubber comprises the following raw materials in parts by weight: 60-80 parts of halogenated butyl rubber, 10-30 parts of natural rubber, 10-20 parts of styrene-butadiene rubber, 10-40 parts of N326 carbon black, 20-50 parts of semi-reinforcing carbon black, 3-5 parts of dibutyl phthalate, 0.5-2 parts of stearic acid, 3-5 parts of zinc oxide, 0-1 part of magnesium oxide, 1-3 parts of tackifying resin, 1-2 parts of homogenizing agent, 1.5-2 parts of antioxidant, 0.5-2 parts of accelerator, 1-2 parts of insoluble sulfur and 0-0.5 parts of anti-scorch agent. The natural rubber is graphene masterbatch, or graphene masterbatch and smoke sheet rubber. The graphene-enhanced airtight layer rubber for aircraft tires provided by the present invention adopts graphene masterbatch to introduce graphene components, effectively realizing the uniform dispersion of two-dimensional layered nanographene in the airtight layer rubber, and can improve the gas barrier performance of the airtight layer rubber; at the same time, the raw rubber system in the present invention comprises halogenated butyl rubber, natural rubber and styrene-butadiene rubber, wherein halogenated butyl rubber is the main raw rubber system component, and its gas barrier performance is excellent, and it has good flexibility and weather resistance, but its scorch safety is poor and its processing technology is poor; therefore, the present invention uses natural rubber and styrene-butadiene rubber in a compounded manner, and the natural rubber has high strength and good processing performance; styrene-butadiene rubber has good aging resistance, heat resistance and processing performance, and the use of the three in the present invention can effectively improve the strength, aging resistance, scorch safety and processing performance of the rubber. At the same time, the present invention also helps to further improve the viscosity of the semi-finished product of the mixed rubber through dibutyl phthalate and tackifying resin, thereby improving the processing technology performance. The present invention adopts stearic acid and zinc oxide as vulcanization activators, and at the same time, zinc oxide can also improve the mechanical properties and anti-aging properties of the rubber. In the present invention, the reinforcement system uses N326 carbon black and part of the semi-reinforcing carbon black; through the compounding of N326 carbon black and semi-reinforcing carbon black, the mechanical properties of the rubber mix (including tensile strength, elongation at break, 300% tensile stress, and Shore A hardness) can be effectively improved, and the processing performance of the rubber mix can be improved, so that the rubber mix has high elasticity, low heat generation, and good dynamic performance. In summary, the present invention uses graphene masterbatch to effectively improve the air tightness of the rubber mix, and as an airtight layer glue, it can maintain the stability of the internal air pressure of the aircraft tire for a long time, and can effectively ensure the safety of the aircraft tire. At the same time, the graphene-enhanced airtight layer glue for aircraft tires provided by the present invention has a reasonable setting of the formula, and the mechanical properties (including tensile strength, elongation at break, 300% tensile stress, Shore A hardness) and aging resistance and other properties are also significantly improved. DETAILED DESCRIPTION

[0037] The present invention provides a graphene-reinforced airtight layer adhesive for aviation tires, comprising the following raw materials in parts by weight:

[0038] 60-80 parts of halogenated butyl rubber, 10-30 parts of natural rubber, 10-20 parts of styrene-butadiene rubber, 10-40 parts of N326 carbon black, 20-50 parts of semi-reinforcing carbon black, 3-5 parts of dibutyl phthalate, 0.5-2 parts of stearic acid, 3-5 parts of zinc oxide, 0-1 part of magnesium oxide, 1-3 parts of tackifying resin, 1-2 parts of leveling agent, 1.5-2 parts of antioxidant, 0.5-2 parts of accelerator, 1-2 parts of insoluble sulfur, 0-0.5 parts of scorch retarder;

[0039] The natural rubber is graphene masterbatch, or graphene masterbatch and smoked sheet rubber.

[0040] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0041] In terms of mass fraction, the raw materials for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided by the present invention include 60 to 80 parts of halogenated butyl rubber, preferably 65 to 75 parts, and in the embodiment, 70 parts. In the present invention, the halogenated butyl rubber preferably includes brominated butyl rubber and / or chlorinated butyl rubber.

[0042] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the airtight layer rubber for graphene-enhanced aircraft tires provided by the present invention include 10 to 30 parts of natural rubber, preferably 15 to 25 parts, and in the embodiment, it can be 20 parts. In the present invention, the natural rubber is a graphene masterbatch, or a graphene masterbatch and a smoke sheet rubber. The graphene masterbatch is preferably purchased from Changzhou Sixth Element Materials Technology Co., Ltd. The smoke sheet rubber is preferably 1# smoke sheet rubber.

[0043] The present invention introduces two-dimensional layered nano-carbon material graphene as a filler into the graphene-enhanced airtight layer rubber for aircraft tires through graphene masterbatch. In addition to having excellent mechanical properties, its layered structure can effectively extend the diffusion path of gas molecules in the rubber matrix and improve the gas barrier performance of the rubber. However, the surface of the two-dimensional layered nano-carbon material graphene is in an inert state, and the interaction with other media is weak, and there is a van der Waals force between the layers, which makes it very easy to stack and agglomerate between the layers, resulting in difficulty in dispersing it in the rubber matrix, affecting the further performance of its performance. The present invention uses graphene masterbatch as a raw material to achieve a uniform distribution of the two-dimensional layered nano-carbon material graphene in the mixed rubber, thereby effectively improving the airtightness and mechanical properties of the graphene-enhanced airtight layer rubber for aircraft tires.

[0044] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the airtight layer rubber for the graphene-reinforced aircraft tire provided by the present invention include 10 to 20 parts of styrene-butadiene rubber, preferably 10 to 15 parts, and in the embodiment it can be 10 parts.

[0045] The present invention provides a method for further improving the strength, aging resistance, scorch safety and processing performance of graphene-reinforced airtight layer rubber for aviation tires by controlling the mass ratio of halogenated butyl rubber, natural rubber and styrene-butadiene rubber in the raw rubber system.

[0046] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-reinforced airtight layer rubber for aircraft tires provided by the present invention include 10 to 40 parts of N326 carbon black, preferably 15 to 30 parts, and in the embodiment, it can be 20 parts.

[0047] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-reinforced airtight layer rubber for aircraft tires provided by the present invention include 20 to 50 parts of semi-reinforcing carbon black, preferably 25 to 45 parts, and in the embodiment, it can be 40 parts.

[0048] In the present invention, N326 carbon black is a low-structured, highly wear-resistant carbon black that can make the rubber mix have higher mechanical properties. Semi-reinforcing carbon black is a high-structured carbon black that can improve the processing performance of the rubber compound, and its vulcanized rubber has high elasticity, low heat generation, and good dynamic performance. The present invention can further improve the mechanical properties of the rubber mix, including tensile strength, elongation at break, 300% tensile stress, and Shore A hardness, by controlling the mass ratio of the N326 carbon black and the semi-reinforcing carbon black.

[0049] Based on the mass fraction of the halogenated butyl rubber, the raw material for preparing the airtight layer rubber for graphene-enhanced aircraft tires provided by the present invention includes 3 to 5 parts of dibutyl phthalate, preferably 4 to 5 parts, and specifically 5 parts in the embodiment. By adding dibutyl phthalate and controlling the mass fraction of the dibutyl phthalate, the present invention can further improve the viscosity of the semi-finished product of the mixed rubber and improve the processing performance.

[0050] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-reinforced airtight layer rubber for aircraft tires provided by the present invention include 0.5 to 2 parts of stearic acid, preferably 1 to 2 parts, and in the embodiment it can be 2 parts.

[0051] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-reinforced airtight layer rubber for aircraft tires provided by the present invention include 3 to 5 parts of zinc oxide, preferably 4 to 5 parts, and in the embodiment, it can be 5 parts.

[0052] The present invention adopts stearic acid and zinc oxide as the vulcanization activator, and controls the preparation ratio of stearic acid and zinc oxide, which is also beneficial for zinc oxide to further improve the mechanical properties and anti-aging properties of the mixed rubber.

[0053] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided by the present invention include 0 to 1 part of magnesium oxide, preferably 0 to 0.8 part, and in the embodiment, it can be 0.5 part. In the present invention, the magnesium oxide acts as an acid absorber and also has an anti-scorch effect, which can improve the processing safety of the mixed rubber.

[0054] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the airtight layer rubber for graphene-enhanced aircraft tires provided by the present invention include 1 to 3 parts of tackifying resin, preferably 1.5 to 2.5 parts, and in the embodiment, it can be 2 parts. In the present invention, the tackifying resin is preferably SP1068. By adding the tackifying resin and controlling the mass fraction of the tackifying resin, the present invention can further improve the viscosity of the semi-finished product of the mixed rubber and improve the processing performance.

[0055] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the airtight layer rubber for graphene-enhanced aircraft tires provided by the present invention include 1 to 2 parts of a homogenizer, preferably 1.5 to 2 parts. In the present invention, the homogenizer is preferably 40MSF. In the present invention, the addition of the homogenizer 40MSF is beneficial to improving the mixing uniformity of the halogenated butyl rubber and the natural rubber, and obtaining a high-performance mixed rubber.

[0056] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the airtight layer rubber for graphene-enhanced aircraft tires provided by the present invention include 1.5 to 2 parts of antioxidants, and in the embodiment, it can be 1.5 parts or 2 parts. In the present invention, the antioxidant is preferably a p-phenylenediamine antioxidant, and the p-phenylenediamine antioxidant preferably includes antioxidant 4010NA and / or antioxidant 4020. The antioxidant 4010NA and antioxidant 4020 have particularly good protective effects on ozone aging and flex cracking, and are also excellent protective agents for heat, oxygen, light, etc. and general aging.

[0057] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the airtight layer rubber for graphene-enhanced aircraft tires provided by the present invention include 0.5 to 2 parts of accelerators, preferably 1 to 2 parts, more preferably 1.3 to 1.6 parts, and in the embodiment, it can be 1.4 parts. In the present invention, the accelerator includes one or more of thiazole accelerators, sulfonamide accelerators and thiuram accelerators. The thiazole accelerator preferably includes accelerator DM and / or accelerator M. The sulfonamide accelerator preferably includes one or more of accelerator NOBS, accelerator DZ and accelerator CZ. The thiuram accelerator preferably includes one or more of accelerator TETD, accelerator TMTD and accelerator TBTD. The accelerator more preferably includes at least two of accelerator DM, accelerator M, accelerator NOBS, accelerator DZ, accelerator CZ, accelerator TETD, accelerator TMTD and accelerator TBTD, and in the embodiment, it can be accelerator TETD and accelerator NOBS. In the present invention, when the accelerator is preferably two of the above substances, the mass ratio of any two accelerators is preferably 0.6-0.8:0.6. In the present invention, the thiuram accelerator can increase the vulcanization rate of the rubber compound, and is preferably used together with the thiazole accelerator and / or the sulfenamide accelerator.

[0058] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided by the present invention include 1 to 2 parts of insoluble sulfur, and in the embodiment, it can be 1 part. In the present invention, the insoluble sulfur is IS-60. The insoluble sulfur IS-60 can effectively prevent sulfur from spraying out of the surface of the mixed rubber.

[0059] Based on the mass fraction of the halogenated butyl rubber, the raw materials for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided by the present invention include 0 to 0.5 parts of an anti-scorch agent, which may be 0 parts, 0.1 parts or 0.3 parts in the embodiment. In the present invention, the anti-scorch agent is preferably an anti-scorch agent CTP. The addition of the anti-scorch agent CTP can prolong the scorch time of the mixed rubber without affecting the structure and performance of the vulcanized rubber.

[0060] In the present invention, the graphene-enhanced airtight layer rubber for aircraft tires preferably includes the following raw materials in parts by mass:

[0061] 70-80 parts of chlorinated butyl rubber, 10-20 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 20-30 parts of N326 carbon black, 30-40 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0-1 part of magnesium oxide, 2 parts of tackifying resin SP1068, 1.5-2 parts of leveling agent 40MSF, 1.5-2 parts of antioxidant, 0.5-0.8 parts of accelerator TETD, 0-0.6 parts of accelerator NOBS, 0-1 parts of accelerator DM, 0.6-1 parts of insoluble sulfur, and 0-0.3 parts of scorch retarder CTP.

[0062] As a specific embodiment of the present invention, the graphene-reinforced airtight layer rubber for aircraft tires includes the following raw materials in parts by mass:

[0063] 70 parts of chlorinated butyl rubber, 20 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur, and 0.3 parts of scorch retarder CTP.

[0064] As a specific embodiment of the present invention, the graphene-reinforced airtight layer rubber for aircraft tires includes the following raw materials in parts by mass:

[0065] 80 parts of brominated butyl rubber, 10 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 30 parts of N326 carbon black, 30 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of magnesium oxide, 2 parts of tackifying resin SP1068, 1.5 parts of leveling agent 40MSF, 2 parts of antioxidant 4020, 0.5 parts of accelerator TMTD, 1 part of accelerator DM, and 0.6 parts of insoluble sulfur.

[0066] The present invention provides a method for preparing the graphene-reinforced airtight layer adhesive for aircraft tires described in the above technical solution, comprising the following steps:

[0067] Step 1, putting halogenated butyl rubber, natural rubber, styrene-butadiene rubber, a homogenizer and a tackifying resin into an internal mixer according to a certain proportion, and mixing and kneading;

[0068] Step 2, adding the antioxidant and stearic acid into the internal mixer according to the proportion, and mixing and kneading;

[0069] Step 3, adding N326 carbon black, semi-reinforcing carbon black and dibutyl phthalate into the internal mixer described in step 1 according to a certain proportion, and mixing and kneading;

[0070] Step 4, discharging the mixture obtained in step 3 from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber;

[0071] Step 5, after the first rubber mix is ​​placed aside, insoluble sulfur, magnesium oxide, zinc oxide, accelerator and scorch retarder are put into an internal mixer according to a proportion with the first rubber mix, and mixed and kneaded;

[0072] Step six, discharge the mixture obtained in step five from the internal mixer to a tablet press, cool it, and place it aside to obtain a graphene-enhanced airtight layer compound for aircraft tires.

[0073] In the present invention, the mixing and kneading temperature in step 1 is preferably increased to 110°C.

[0074] In the present invention, the mixing and kneading temperature in step 2 is preferably increased from 110°C to 120°C.

[0075] In the present invention, the mixing and kneading temperature in step 3 is preferably increased from 120°C to 140°C;

[0076] In the present invention, in step 5, the parking time is preferably 16 to 24 hours. The present invention preferably parks the first-stage mixed rubber, and controls the parking time to be preferably 16 to 24 hours, which is conducive to further uniform dispersion of the additives (including homogenizer, tackifying resin, antioxidant, stearic acid, N326 carbon black, semi-reinforcing carbon black and dibutyl phthalate) in the first-stage mixed rubber, adsorbing and affinity with the rubber macromolecular chains in the first-stage mixed rubber, forming more inclusive rubber, thereby improving the reinforcement effect on the rubber.

[0077] In the present invention, in step 5: when the mass fraction of the magnesium oxide and / or the anti-scorching agent is 0, the magnesium oxide and / or the anti-scorching agent is omitted in step 5. The mixing and kneading temperature in step 5 is preferably 100°C.

[0078] In the present invention, after obtaining the graphene-enhanced aircraft tire airtight layer rubber mix in step 6, the present invention preferably further comprises: step 7, vulcanizing the graphene-enhanced aircraft tire airtight layer rubber mix to obtain the graphene-enhanced aircraft tire airtight layer rubber. The vulcanization temperature is preferably 135-155°C, more preferably 155°C; the vulcanization pressure is preferably 0.2-20MPa, more preferably 10MPa.

[0079] The preparation method provided by the present invention adopts the above-mentioned reasonable mixing and kneading steps, and at the same time controls the temperature parameters of each step in the mixing and kneading, which can match the formula of the airtight layer glue for graphene enhanced aircraft tires, ensure the quality of glue removal, and obtain the airtight layer glue for graphene enhanced aircraft tires with excellent performance.

[0080] The graphene-enhanced airtight layer adhesive for aircraft tires provided by the present invention has excellent gas barrier properties, good mechanical properties, and excellent aging resistance. When applied to the airtight layer adhesive for aircraft tires, it can maintain the stability of the internal air pressure of the aircraft tire for a long time, and can effectively ensure the safety of the aircraft tire in use.

[0081] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0082] In the following embodiments: graphene masterbatch was purchased from Changzhou Sixth Element Material Technology Co., Ltd., graphene powder was purchased from Changzhou Sixth Element Material Technology Co., Ltd., and graphene oxide powder was purchased from Changzhou Sixth Element Material Technology Co., Ltd.

[0083] Example 1

[0084] This embodiment provides a graphene-reinforced airtight layer rubber for aircraft tires, comprising the following raw materials in parts by weight:

[0085] 70 parts of chlorinated butyl rubber, 20 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur IS-60, and 0.3 parts of scorch retarder CTP.

[0086] The method for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided in this embodiment comprises the following steps:

[0087] Step 1: put chlorinated butyl rubber, graphene masterbatch, styrene-butadiene rubber, homogenizer 40MSF and tackifying resin SP1068 into an internal mixer according to the above mass parts, mix and knead, and raise the mixing temperature to 110° C.;

[0088] Step 2, adding antioxidant 4010NA and stearic acid according to the above mass fractions into the internal mixer described in step 1, mixing and kneading, and the mixing temperature is increased from 110° C. to 120° C.;

[0089] Step 3, adding N326 carbon black, semi-reinforcing carbon black and dibutyl phthalate according to the above mass fractions into the internal mixer described in step 1, mixing and kneading, and the mixing temperature is increased from 120° C. to 140° C.;

[0090] Step 4: When the mixing temperature reaches 140°C, the mixture is discharged from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber;

[0091] Step 5, after the first-stage rubber mix is ​​left for 24 hours, the insoluble sulfur IS-60, zinc oxide, magnesium oxide, accelerator TETD, accelerator NOBS and scorch retarder CTP are put into an internal mixer according to the above mass fractions with the first-stage rubber mix, and the mixing and mixing temperature is 100°C;

[0092] Step six, discharge the mixture obtained in step five from the internal mixer to the tablet press, cool it, and leave it to stand. The obtained mixture is the final rubber mix, that is, the graphene-enhanced airtight layer mixed rubber for aircraft tires is obtained.

[0093] Comparative Example 1

[0094] This embodiment provides a graphene-reinforced airtight layer rubber for aircraft tires, comprising the following raw materials in parts by weight:

[0095] 70 parts of chlorinated butyl rubber, 20 parts of 1# smoke sheet rubber, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 0.8 parts of graphene powder, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur IS-60, and 0.3 parts of scorch retarder CTP.

[0096] The method for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided in this embodiment comprises the following steps:

[0097] Step 1: put chlorinated butyl rubber, 1# cigarette sheet rubber, styrene-butadiene rubber, homogenizer 40MSF and tackifying resin SP1068 according to the above mass parts into an internal mixer, mix and knead, and raise the mixing temperature to 110° C.;

[0098] Step 2, adding antioxidant 4010NA and stearic acid according to the above mass fractions into the internal mixer described in step 1, mixing and kneading, and the mixing temperature is increased from 110° C. to 120° C.;

[0099] Step 3: Add N326 carbon black, graphene powder and dibutyl phthalate according to the above mass fractions into the internal mixer described in step 1, mix and knead, and increase the mixing temperature from 120° C. to 140° C.;

[0100] Step 4: When the mixing temperature reaches 140°C, the mixture is discharged from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber;

[0101] Step 5, after the first-stage rubber mix is ​​left for 24 hours, the insoluble sulfur IS-60, zinc oxide, magnesium oxide, accelerator TETD, accelerator NOBS and scorch retarder CTP are put into an internal mixer according to the above mass fractions with the first-stage rubber mix, and the mixing and mixing temperature is 100°C;

[0102] Step six, discharge the mixture obtained in step five from the internal mixer to the tablet press, cool it, and leave it to stand. The obtained mixture is the final rubber mix, that is, the graphene-enhanced airtight layer mixed rubber for aircraft tires is obtained.

[0103] Comparative Example 2

[0104] This embodiment provides a graphene-reinforced airtight layer rubber for aircraft tires, comprising the following raw materials in parts by weight:

[0105] 70 parts of chlorinated butyl rubber, 20 parts of 1# smoke sheet rubber, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 0.8 parts of graphene oxide powder, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur IS-60, and 0.3 parts of scorch retarder CTP.

[0106] The method for preparing the graphene-enhanced airtight layer rubber for aircraft tires provided in this embodiment comprises the following steps:

[0107] Step 1: put chlorinated butyl rubber, 1# cigarette sheet rubber, styrene-butadiene rubber, homogenizer 40MSF and tackifying resin SP1068 according to the above mass parts into an internal mixer, mix and knead, and raise the mixing temperature to 110° C.;

[0108] Step 2, adding antioxidant 4010NA and stearic acid according to the above mass fractions into the internal mixer described in step 1, mixing and kneading, and the mixing temperature is increased from 110° C. to 120° C.;

[0109] Step 3: Add N326 carbon black, graphene oxide powder, and dibutyl phthalate according to the above mass fractions into the internal mixer described in step 1, mix and knead, and increase the mixing temperature from 120° C. to 140° C.;

[0110] Step 4: When the mixing temperature reaches 140°C, the mixture is discharged from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber;

[0111] Step 5, after the first-stage rubber mix is ​​left for 24 hours, the insoluble sulfur IS-60, zinc oxide, magnesium oxide, accelerator TETD, accelerator NOBS and scorch retarder CTP are put into an internal mixer according to the above mass fractions with the first-stage rubber mix, and the mixing and mixing temperature is 100°C;

[0112] Step six, discharge the mixture obtained in step five from the internal mixer to the tablet press, cool it, and leave it to stand. The obtained mixture is the final rubber mix, that is, the graphene-enhanced airtight layer mixed rubber for aircraft tires is obtained.

[0113] Comparative Example 3

[0114] This comparative example provides a rubber compound, comprising the following raw materials in parts by weight:

[0115] 70 parts of chlorinated butyl rubber, 20 parts of 1# smoked sheet rubber, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur IS-60, and 0.3 parts of scorch retarder CTP.

[0116] The preparation method of the rubber compound provided in this comparative example comprises the following steps:

[0117] Step 1: put chlorinated butyl rubber, 1# cigarette sheet rubber, and styrene-butadiene rubber into an internal mixer according to the above mass parts, mix and knead, and raise the mixing temperature to 110° C.;

[0118] Step 2, adding antioxidant 4010NA and stearic acid according to the above mass fractions into the internal mixer described in step 1, mixing and kneading, and the mixing temperature is increased from 110° C. to 120° C.;

[0119] Step 3, adding N326 carbon black, semi-reinforcing carbon black and dibutyl phthalate according to the above mass fractions into the internal mixer described in step 1, mixing and kneading, and the mixing temperature is increased from 120° C. to 140° C.;

[0120] Step 4: When the mixing temperature reaches 140°C, the mixture is discharged from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber;

[0121] Step 5, after the first-stage rubber mix is ​​left for 24 hours, the insoluble sulfur IS-60, zinc oxide, magnesium oxide, accelerator TETD, accelerator NOBS and scorch retarder CTP are put into an internal mixer according to the above mass fractions with the first-stage rubber mix, and the mixing and mixing temperature is 100°C;

[0122] Step 6, discharge the mixture obtained in step 5 from the internal mixer to the tablet press, cool it, and leave it to stand. The obtained mixture is the final rubber mix, that is, the mixed rubber is obtained.

[0123] The performance of the vulcanized rubber compounds obtained in Example 1 and Comparative Examples 1 to 3 was tested, and the test results are listed in Table 1. The formula of Comparative Example 3 does not contain graphene powder or graphene oxide powder.

[0124] Table 1 Performance test results of graphene-enhanced airtight layer rubber for aircraft tires prepared in Example 1 and Comparative Examples 1 to 3

[0125]

[0126]

[0127] Note: The vulcanization temperature is 155°C and the pressure is 10MPa.

[0128] It can be seen from the data in Table 1 that the graphene-enhanced airtight layer adhesive for aircraft tires provided by the present invention as an airtight layer adhesive for aircraft tires has significantly improved air tightness, mechanical properties, aging resistance and other properties compared to the airtight layer adhesives in the existing technology, thereby being able to maintain the stability of the internal air pressure of the aircraft tire for a long time, and effectively ensuring the safety of the use of the aircraft tire.

[0129] It can be seen from the above embodiments that the present invention uses graphene masterbatch to effectively improve the air tightness of the mixed rubber. As an airtight layer rubber, it can maintain the stability of the internal air pressure of the aircraft tire for a long time, and can effectively ensure the safety of the aircraft tire. At the same time, the graphene-enhanced airtight layer rubber for aircraft tires provided by the present invention has a reasonable formula setting, and the mechanical properties (including tensile strength, elongation at break, 300% tensile stress, Shore A hardness) and aging resistance are also significantly improved.

[0130] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A graphene-enhanced airtight layer rubber for aircraft tires, characterized in that: The preparation comprises the following raw materials in parts by weight: 60-80 parts of halogenated butyl rubber, 10-30 parts of natural rubber, 10-20 parts of styrene-butadiene rubber, 10-40 parts of N326 carbon black, 20-50 parts of semi-reinforcing carbon black, 3-5 parts of dibutyl phthalate, 0.5-2 parts of stearic acid, 3-5 parts of zinc oxide, 0-1 part of magnesium oxide, 1-3 parts of tackifying resin, 1-2 parts of leveling agent, 1.5-2 parts of antioxidant, 0.5-2 parts of accelerator, 1-2 parts of insoluble sulfur, 0-0.5 parts of scorch retarder; The natural rubber is graphene masterbatch, or graphene masterbatch and smoked sheet rubber.

2. The graphene-enhanced inner liner adhesive for aircraft tires according to claim 1, characterized in that: The halogenated butyl rubber includes brominated butyl rubber and / or chlorinated butyl rubber.

3. The graphene-enhanced inner liner rubber for aircraft tire according to claim 1, characterized in that: The tackifying resin is SP1068; The homogenizer is 40MSF; The antioxidant is a p-phenylenediamine antioxidant; The accelerator includes one or more of thiazole accelerators, sulfenamide accelerators and thiuram accelerators; The insoluble sulfur is IS-60; The anti-scorching agent is anti-scorching agent CTP.

4. The graphene-enhanced inner liner rubber for aircraft tire according to claim 3, characterized in that: The p-phenylenediamine antioxidant includes antioxidant 4010NA and / or antioxidant 4020.

5. The graphene-enhanced airtight layer adhesive for aircraft tire according to claim 3, characterized in that: The thiazole accelerator includes accelerator DM and / or accelerator M; The sulfenamide accelerator includes one or more of accelerator NOBS, accelerator DZ and accelerator CZ; The thiuram accelerator includes one or more of accelerator TETD, accelerator TMTD and accelerator TBTD.

6. The graphene-enhanced inner liner adhesive for aircraft tires according to claim 1, characterized in that: The preparation comprises the following raw materials in parts by weight: 70 parts of chlorinated butyl rubber, 20 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 20 parts of N326 carbon black, 40 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 0.5 parts of magnesium oxide, 2 parts of tackifying resin SP1068, 2 parts of leveling agent 40MSF, 1.5 parts of antioxidant 4010NA, 0.8 parts of accelerator TETD, 0.6 parts of accelerator NOBS, 1 part of insoluble sulfur, and 0.3 parts of scorch retarder CTP.

7. The graphene-enhanced inner liner adhesive for aircraft tires according to claim 1, characterized in that: Includes the following mass raw materials: 80 parts of brominated butyl rubber, 10 parts of graphene masterbatch, 10 parts of styrene-butadiene rubber, 30 parts of N326 carbon black, 30 parts of semi-reinforcing carbon black, 5 parts of dibutyl phthalate, 2 parts of stearic acid, 5 parts of zinc oxide, 1 part of magnesium oxide, 2 parts of tackifying resin SP1068, 1.5 parts of leveling agent 40MSF, 2 parts of antioxidant 4020, 0.5 parts of accelerator TMTD, 1 part of accelerator DM, and 0.6 parts of insoluble sulfur.

8. The method for preparing the graphene-reinforced airtight layer rubber for aircraft tires according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1, putting halogenated butyl rubber, natural rubber, styrene-butadiene rubber, a homogenizer and a tackifying resin into an internal mixer according to a certain proportion, and mixing and kneading; Step 2, adding the antioxidant and stearic acid into the internal mixer according to the proportion, and mixing and kneading; Step 3, adding N326 carbon black, semi-reinforcing carbon black and dibutyl phthalate into the internal mixer described in step 1 according to a certain proportion, and mixing and kneading; Step 4, discharging the mixture obtained in step 3 from the internal mixer to the upper and lower sheets of the tablet press to form a mixed rubber; Step 5, after the first rubber mix is ​​placed aside, insoluble sulfur, magnesium oxide, zinc oxide, accelerator and scorch retarder are put into an internal mixer according to a proportion with the first rubber mix, and mixed and kneaded; Step six, discharge the mixture obtained in step five from the internal mixer to a tablet press, cool it, and place it aside to obtain a graphene-enhanced airtight layer compound for aircraft tires.

9. The preparation method according to claim 8, characterized in that: In step 1, the mixing and kneading temperature is raised to 110°C; In step 2, the mixing and kneading temperature is increased from 110°C to 120°C; In step 3, the mixing and kneading temperature is increased from 120°C to 140°C.

10. The preparation method according to claim 8, characterized in that: The parking time is 16 to 24 hours; In step 5, the mixing and kneading temperature is increased to 100°C.

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