Composite Reinforcing Material, Bromobutyl Rubber Composite Material, Preparation Method and Application Thereof

Abstract

The present invention discloses a composite reinforcing material, a bromobutyl rubber composite material, and a preparation method and application thereof. The composite reinforcing material comprises organic clay and a carrier; the carrier has a transitional structure of chain-like and layered structures. The organic clay and the carrier are uniformly mixed to obtain the composite reinforcing material. The bromobutyl rubber composite material comprises the composite reinforcing material and bromobutyl rubber; the bromobutyl rubber solution and the dispersion of the composite reinforcing material are uniformly mixed, the solvent is removed, dried, additives are added, kneaded, and vulcanized to obtain the bromobutyl rubber composite material. The present invention utilizes a carrier with a special structure (such as sepiolite) to improve the dispersion of the organic clay, effectively preventing the agglomeration of the organic clay and greatly improving the performance of the bromobutyl rubber composite material.

Description

Technical Field

[0001] The present invention relates to the technical field of organic clay / rubber nanocomposites. Further, it relates to a composite reinforcing material, a bromobutyl rubber composite material, and their preparation methods and applications. Background Art

[0002] Bromobutyl rubber (BIIR) is a product obtained by halogenating and modifying butyl rubber. Based on traditional butyl rubber, bromobutyl rubber improves the activity of the double bonds of butyl rubber, improves its compatibility with unsaturated rubbers, enhances self-adhesion and co-crosslinking ability, while maintaining the original properties of butyl rubber. After modification, the performance of bromobutyl rubber is further improved. Among them, the dispersibility of the reinforcing material is the key to improving the performance of rubber. Therefore, improving the dispersibility of the reinforcing material is the difficulty and focus in the preparation of bromobutyl rubber composite materials.

[0003] Organic clay (OC) has a unique lamellar structure. By uniformly dispersing nanoscale OC in BIIR, an organic clay / bromobutyl rubber composite material with excellent airtightness and mechanical properties can be obtained.

[0004] However, in the existing organic clay / bromobutyl rubber composite materials, there are problems such as agglomeration of organic clay and uneven dispersion, which cannot effectively improve the performance of bromobutyl rubber composite materials. Summary of the Invention

[0005] To solve the problems in the prior art, the present invention provides a composite reinforcing material, a bromobutyl rubber composite material, and their preparation methods and applications. The present invention uses a carrier with a special structure (such as sepiolite) to improve the dispersibility of organic clay, effectively preventing the agglomeration of organic clay and greatly improving the performance of bromobutyl rubber composite materials.

[0006] One object of the present invention is to provide a composite reinforcing material, which includes organic clay and a carrier; the carrier has a transitional structure of chain-like and lamellar.

[0007] In the composite reinforcing material of the present invention, preferably,

[0008] the carrier is an inorganic carrier, preferably sepiolite; and / or,

[0009] the mass ratio of organic clay to the carrier is 1:(0.01 - 1); such as 1:0.01, 1:0.02, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1 and any range composed of any two points, more preferably 1:(0.1 - 0.5);

[0010] Further preferably,

[0011] the particle size of the sepiolite ≥ 200 mesh; preferably 200 - 500 mesh, most preferably 400 mesh; and / or,

[0012] the organic clay is selected from the organic clay obtained by organically modifying layered silicate with quaternary ammonium salt. In the present invention, the organic clay is selected from the organic clay obtained by organically modifying layered silicate with 17 [[CH3(CH2)]]NH3 + ; the organic clay used in the present invention can be directly purchased or prepared by existing methods. Preferably, the organic clay used in the present invention (1.30P, the modifier is [[CH3(CH2)]]NH3 17 [[CH3(CH2)]]NH3 + ), is purchased from NANOCOR Company, USA.

[0013] The present invention discovers that sepiolite is a hydrated layered silicate mineral, and sepiolite has a crystal structure with continuous silicon - oxygen tetrahedron layers. Among them, each silicon - oxygen tetrahedron shares two apexes and is connected to three adjacent tetrahedrons, having unique chain - like and layered transitional structural characteristics. This unique structure makes sepiolite a good carrier. Therefore, sepiolite can uniformly disperse the organic clay in the rubber system, effectively preventing the agglomeration of the organic clay and greatly improving the performance of the bromobutyl rubber composite material.

[0014] The second object of the present invention is to provide a preparation method of a composite reinforcing material as described in the first object of the present invention, by uniformly mixing the organic clay and the carrier to obtain the composite reinforcing material.

[0015] When the composite reinforcing material of the present invention is applied, it can be directly added or, according to the nature of the substrate to be added, prepared into a uniformly dispersed mixed solution and then added. Specifically, it can be judged according to the common knowledge of those skilled in the art based on the matrix situation during use.

[0016] The third object of the present invention is to provide a bromobutyl rubber composite material, which includes the composite reinforcing material and bromobutyl rubber;

[0017] The composite reinforcing material is selected from the composite reinforcing material described in the first object of the present invention or the composite reinforcing material prepared by the method described in the second object of the present invention.

[0018] In the bromobutyl rubber composite material described in the present invention, preferably,

[0019] Based on 100 parts by weight of bromobutyl rubber, the addition amount of the organic clay in the composite reinforcing material is 1 to 15 parts by weight; for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by weight and any range composed of any two points, more preferably 3 to 10 parts by weight.

[0020] The fourth object of the present invention is to provide a preparation method of a bromobutyl rubber composite material, comprising the following steps:

[0021] Mix the bromobutyl rubber solution and the dispersion of the composite reinforcing material evenly, remove the solvent, dry, add additives, knead, and vulcanize to obtain the bromobutyl rubber composite material;

[0022] Preferably, the bromobutyl rubber composite material described in the third object of the present invention is prepared.

[0023] In the present invention, the preparation process of the bromobutyl rubber composite material can adopt the common rubber processing processes in the prior art. The equipment used is also the equipment in rubber processing in the prior art, such as internal mixers, open mills, vulcanizers, etc.

[0024] In the present invention, common additives in the art can be added as needed during the preparation of the bromobutyl rubber composite material, such as zinc oxide, anti-aging agents (such as anti-aging agent D), reinforcing agents (such as carbon black, white carbon black), accelerators (such as accelerator DM), sulfur, silane coupling agents (such as Si69), etc., and their dosages are all conventional dosages or can be adjusted according to requirements.

[0025] In the preparation method of the bromobutyl rubber composite material described in the present invention, preferably,

[0026] The preparation method of the bromobutyl rubber solution is: <s

[0027] Add bromobutyl rubber to an organic solvent and mix evenly to obtain a bromobutyl rubber solution;

[0028] Preferably,

[0029] The mass concentration of the bromobutyl rubber solution is 10% to 20%; when the mass fraction exceeds 20%, the solution viscosity is high, which is not conducive to post-treatment; when the mass fraction is less than 10%, it will cause waste of the solvent; and / or,

[0030] The organic solvent is an alkane solvent, preferably n-hexane; and / or,

[0031] The mixing temperature is 10 to 80 °C; more preferably 20 to 60 °C; and / or,

[0032] The mixing time is 0.5 to 8 h; more preferably 1 to 3 h.

[0033] In the preparation method of the brominated butyl rubber composite material according to the present invention, preferably,

[0034] The preparation method of the dispersion of the composite reinforcing material is as follows:

[0035] Mix the organic clay and the carrier uniformly in an organic solvent; in the present invention, the organic clay and the carrier (such as sepiolite) are added together to an organic solvent such as n-hexane to form a dispersion. Since both the organic clay and the carrier are inorganic substances, their solubility in n-hexane is relatively low. When preparing the dispersion, first mix the organic clay and the carrier powder uniformly, add them together to the n-hexane solution, and assist with stirring until the organic clay and sepiolite are uniformly dispersed in n-hexane;

[0036] More preferably,

[0037] The organic solvent is an alkane solvent, preferably n-hexane; and / or,

[0038] The mass-volume ratio of the organic clay to the organic solvent is (1-15):100; and / or,

[0039] The mixing temperature is 10-80°C; further preferably 20-60°C; and / or,

[0040] The mixing time is 0.5-8 h; further preferably 1-6 h.

[0041] In the preparation method of the brominated butyl rubber composite material according to the present invention, preferably,

[0042] When mixing the brominated butyl rubber solution and the dispersion of the composite reinforcing material uniformly,

[0043] The mixing temperature is 10-80°C; preferably 10-35°C; and / or,

[0044] The mixing time is 0.5-8 h; preferably 2-4 h; and / or,

[0045] Remove the organic solvent by boiling the rubber.

[0046] In the present invention, the brominated butyl rubber solution and the organic clay / sepiolite dispersion are mixed together and stirred. By stirring, the organic clay and sepiolite can be uniformly dispersed in the rubber solution to form a more compact hybrid filler network.

[0047] In the preparation method of the brominated butyl rubber composite material according to the present invention, most preferably, it includes the following steps:

[0048] (1) Preparation of rubber solution: At a temperature of 10 - 80 °C, an appropriate amount of bromobutyl rubber is added to n - hexane and stirred for 0.5 - 8 h at an appropriate stirring speed to obtain a rubber solution of bromobutyl rubber.

[0049] (2) Preparation of organic clay and sepiolite dispersion: At a temperature of 10 - 80 °C, an appropriate amount of organic clay and sepiolite are mixed evenly and then added to n - hexane, and stirred for 0.5 - 8 h at an appropriate stirring speed to obtain an organic clay and sepiolite dispersion.

[0050] (3) Take the above - mentioned organic clay and sepiolite dispersion and add it to the above - mentioned bromobutyl rubber solution, stir for 0.5 - 8 h, remove the solvent, dry, add various additives, knead for 1 - 60 min, and then vulcanize to obtain an organic clay / sepiolite / bromobutyl rubber composite material.

[0051] The fifth object of the present invention is to provide an application of the bromobutyl rubber composite material as described in the third object of the present invention or the bromobutyl rubber composite material prepared by the method as described in the fourth object of the present invention as an air - tight layer material, preferably as an air - tight layer material for tires.

[0052] In the ranges and any values disclosed in the present invention, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein. In the following text, in principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.

[0053] Compared with the prior art, the advantages of the present invention are at least as follows:

[0054] (1) By adding a carrier such as (sepiolite), the dispersibility of organic clay in n - hexane is improved, the agglomeration of organic clay is prevented, and thus the dispersion of organic clay in rubber is improved.

[0055] (2) The organic clay / carrier / bromobutyl rubber composite material prepared by this method has excellent mechanical properties and barrier properties. Detailed implementation manners

[0056] The present invention will be specifically described below in combination with specific embodiments. It is necessary to point out here that the following embodiments are only used for further illustration of the present invention and cannot be understood as limiting the protection scope of the present invention. Some non - essential improvements and adjustments made by those skilled in the art based on the content of the present invention still fall within the protection scope of the present invention.

[0057] In addition, it should be noted that the specific technical features described in the following specific embodiments can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0058] In addition, any combination can be made among various different embodiments of the present invention as long as it does not violate the idea of the present invention. The technical solutions thus formed belong to a part of the original public content of this specification and also fall within the protection scope of the present invention.

[0059] Source of raw materials:

[0060] Organic clay (1.30P, with the modifier being [CH3(CH2) 17 NH3 + ), purchased from NANOCOR Company in the United States;

[0061] Sepiolite of 400 mesh, purchased from Hebei Hengguang Mineral Products Co., Ltd.

[0062] If there is no special limitation on the raw materials used in the examples and comparative examples, they are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0063] Testing method:

[0064] Tensile strength / elongation at break is measured according to GB / T528-2009;

[0065] Tear strength is measured according to GB / T529-2008;

[0066] Gas barrier property is measured according to GB1038-2000.

[0067] Example 1

[0068] Weigh 100 g of bromobutyl rubber and 660 g of n-hexane, mix them in a flask, and mechanically stir for 5 h at 25 °C to obtain a bromobutyl rubber solution with a mass fraction of 13.16%.

[0069] Weigh 5 g of organic clay and 0.05 g of sepiolite (400 mesh), mix them evenly in a beaker, then add 100 g of n-hexane, and mechanically stir for 2 h at 25 °C to obtain an organic clay / sepiolite dispersion.

[0070] The organic clay / sepiolite dispersion was added to the bromobutyl rubber solution, mechanically stirred at 25 °C for 2 h, the solvent was removed by boiling, dried, 5 g of zinc oxide, 1 g of stearic acid, 0.5 g of accelerator DM (rubber accelerator DM), 0.7 g of accelerator ZDC (accelerator ZDC) and 0.5 g of sulfur were added, kneaded using a two-roll mill at 20 °C, and vulcanized using a flat vulcanizer at 160 °C to obtain 5 g of an organic clay / 0.05 g of sepiolite / 100 g of bromobutyl rubber composite material.

[0071] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0072] The tensile strength was 6.7 MPa, the tear strength was 19.4 MPa, the elongation at break was 812%, and the gas barrier property was improved by 67%.

[0073] Example 2

[0074] 0.05 g of sepiolite in Example 1 was changed to 0.5 g, and other operations were the same as in Example 1. 5 g of an organic clay / 0.5 g of sepiolite / 100 g of bromobutyl rubber composite material was obtained.

[0075] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0076] The tensile strength was 10.5 MPa, the tear strength was 21.38 MPa, the elongation at break was 975%, and the gas barrier property was improved by 77%.

[0077] Example 3

[0078] 0.05 g of sepiolite in Example 1 was changed to 2.5 g, and other operations were the same as in Example 1. 5 g of an organic clay / 2.5 g of sepiolite / 100 g of bromobutyl rubber composite material was obtained.

[0079] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0080] The tensile strength was 8.9 MPa, the tear strength was 18.44 MPa, the elongation at break was 843%, and the gas barrier property was improved by 68%.

[0081] Example 4

[0082] 0.05 g of sepiolite in Example 1 was changed to 3.5 g, and other operations were the same as in Example 1. 5 g of an organic clay / 3.5 g of sepiolite / 100 g of bromobutyl rubber composite material was obtained.

[0083] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0084] The tensile strength is 8.1 MPa, the tear strength is 17.62 MPa, the elongation at break is 772%, and the gas barrier property is improved by 59%.

[0085] Example 5

[0086] Change 0.05 g of sepiolite in Example 1 to 5 g, and perform other operations in the same manner as in Example 1. Obtain a 5 g organic clay / 5 g sepiolite / 100 g bromobutyl rubber composite material.

[0087] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0088] The tensile strength is 6.9 MPa, the tear strength is 16.65 MPa, the elongation at break is 625%, and the gas barrier property is improved by 45%.

[0089] Example 6

[0090] Change 5 g of organic clay in Example 1 to 1 g, and change 0.05 g of sepiolite to 0.1 g, and perform other operations in the same manner as in Example 1. Obtain a 1 g organic clay / 0.1 g sepiolite / 100 g bromobutyl rubber composite material.

[0091] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0092] The tensile strength is 5.5 MPa, the tear strength is 16.74 MPa, the elongation at break is 741%, and the gas barrier property is improved by 25%.

[0093] Example 7

[0094] Change 5 g of organic clay in Example 1 to 3 g, and change 0.05 g of sepiolite to 0.3 g, and perform other operations in the same manner as in Example 1. Obtain a 3 g organic clay / 0.3 g sepiolite / 100 g bromobutyl rubber composite material.

[0095] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0096] The tensile strength is 6.3 MPa, the tear strength is 17.98 MPa, the elongation at break is 865%, and the gas barrier property is improved by 46%.

[0097] Example 8

[0098] Change 5 g of organic clay in Example 1 to 7 g, and change 0.05 g of sepiolite to 0.7 g, and perform other operations in the same manner as in Example 1. Obtain a 7 g organic clay / 0.7 g sepiolite / 100 g bromobutyl rubber composite material.

[0099] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0100] The tensile strength is 9.1 MPa, the tear strength is 19.71 MPa, the elongation at break is 852%, and the gas barrier property is improved by 69%.

[0101] Example 9

[0102] Change 5 g of the organic clay in Example 1 to 10 g, and change 0.05 g of sepiolite to 1 g. Other operations are the same as in Example 1. A 10 g organic clay / 1 g sepiolite / 100 g bromobutyl rubber composite material is obtained.

[0103] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0104] The tensile strength is 7.9 MPa, the tear strength is 18.4 MPa, the elongation at break is 745%, and the gas barrier property is improved by 62%.

[0105] Example 10

[0106] Change 5 g of the organic clay in Example 1 to 15 g, and change 0.05 g of sepiolite to 1.5 g. Other operations are the same as in Example 1. A 15 g organic clay / 1.5 g sepiolite / 100 g bromobutyl rubber composite material is obtained.

[0107] The properties of the bromobutyl rubber composite material prepared by the above method are as follows:

[0108] The tensile strength is 5.4 MPa, the tear strength is 17.21 MPa, the elongation at break is 696%, and the gas barrier property is improved by 54%.

[0109] Comparative Example 1

[0110] Mix 100 g of bromobutyl rubber, 5 g of zinc oxide, 1 g of stearic acid, 0.5 g of accelerator DM, 0.7 g of accelerator ZDC, and 0.5 g of sulfur according to the steps of Example 1 for mixing and vulcanization to obtain a bromobutyl rubber material.

[0111] The properties of the bromobutyl rubber material prepared by the above method are as follows:

[0112] The tensile strength is 4.29 MPa, the tear strength is 9.31 MPa, the elongation at break is 667%; the gas barrier property is 1.24×10 -14 cm 3 ·cm / cm 2 ·s·pa.

[0113] Comparative Example 2

[0114] Weigh 100 g of bromobutyl rubber and 660 g of n-hexane, mix them in a flask, and mechanically stir at 25 °C for 5 h to obtain a bromobutyl rubber solution with a mass fraction of 13.16%.

[0115] Weigh 5.05 g of organic clay, add it to 100 g of n-hexane, and mechanically stir for 2 h at 25 °C to obtain an organic clay dispersion.

[0116] Add the organic clay dispersion to the bromobutyl rubber solution, mechanically stir for 2 h at 25 °C, remove the solvent by boiling, dry it, add 5 g of zinc oxide, 1 g of stearic acid, 0.5 g of accelerator DM, 0.7 g of accelerator ZDC, and 0.5 g of sulfur, and carry out mixing and vulcanization according to the steps of Example 1 to obtain 5.05 g of organic clay / 100 g of bromobutyl rubber composite.

[0117] The properties of the bromobutyl rubber composite prepared by the above method are as follows:

[0118] The tensile strength is 5.3 MPa, the tear strength is 15.4 MPa, the elongation at break is 784%, and the gas barrier property is increased by 31%.

[0119] Comparative Example 3

[0120] Weigh 100 g of bromobutyl rubber and 660 g of n-hexane, mix them in a flask, and mechanically stir for 5 h at 25 °C to obtain a bromobutyl rubber solution with a mass fraction of 13.16%.

[0121] Weigh 5.05 g of sepiolite (400 mesh), add it to 100 g of n-hexane, and mechanically stir for 2 h at 25 °C to obtain an organic clay dispersion.

[0122] Add the organic clay dispersion to the bromobutyl rubber solution, mechanically stir for 2 h at 25 °C, remove the solvent by boiling, dry it, add 5 g of zinc oxide, 1 g of stearic acid, 0.5 g of accelerator DM, 0.7 g of accelerator ZDC, and 0.5 g of sulfur, and carry out mixing and vulcanization according to the steps of Example 1 to obtain 5.05 g of sepiolite / 100 g of bromobutyl rubber composite.

[0123] The properties of the bromobutyl rubber composite prepared by the above method are as follows:

[0124] The tensile strength is 5.6 MPa, the tear strength is 14.9 MPa, the elongation at break is 841%, and the gas barrier property is increased by 15%.

[0125] By comparing the results of Comparative Example 2 and Comparative Example 3 with those of Example 1, it can be clearly seen that there is a synergistic effect between the organic clay and sepiolite of the present invention, which can effectively improve the comprehensive properties of the bromobutyl rubber composite.

[0126] The present invention has been described in detail above in connection with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, various equivalent substitutions, modifications, or improvements can be made to the technical solutions and their implementation manners of the present invention, and all of these fall within the scope of the present invention. The protection scope of the present invention shall be subject to the appended claims.

[0127] All publications, patent applications, patents, and other references mentioned in this specification are hereby incorporated by reference in their entirety. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0128] When this specification uses prefixes such as "well-known to those skilled in the art", "prior art", or their similar terms to introduce materials, substances, methods, steps, devices, or components, etc., the objects introduced by these prefixes cover those commonly used in the art at the time when this application is filed, but also include those that are not commonly used at present but will become recognized by the art as suitable for similar purposes.

[0129] In the context of this specification, any matters or things not mentioned, except for the explicitly stated content, shall directly apply those known in the art without any changes.

Claims

1. A bromobutyl rubber composite material, characterized in that: The bromobutyl rubber composite material comprises a composite reinforcing material and bromobutyl rubber; The composite reinforcing material comprises organic clay and a carrier; the carrier has a transitional structure of chain-like and layered; The organic clay is selected from the organic clay obtained by organicizing layered silicate with quaternary ammonium salt; The carrier is sepiolite; The mass ratio of the organic clay to the carrier is 1:(0.01 - 1).

2. The bromobutyl rubber composite material according to claim 1, characterized in that: The mass ratio of the organic clay to the carrier is 1:(0.1 - 0.5).

3. The bromobutyl rubber composite material according to claim 1, characterized in that: The particle size of the sepiolite ≥ 200 mesh.

4. The bromobutyl rubber composite material according to claim 3, characterized in that: The particle size of the sepiolite is 200 - 500 mesh.

5. The bromobutyl rubber composite material according to claim 4, characterized in that: The particle size of the sepiolite is 400 mesh.

6. The bromobutyl rubber composite material according to claim 1, characterized in that: The preparation method of the composite reinforcing material is: mixing the organic clay and the carrier evenly to obtain the composite reinforcing material.

7. The bromobutyl rubber composite material according to claim 1, characterized in that: Based on 100 parts by weight of bromobutyl rubber, the addition amount of the organic clay in the composite reinforcing material is 1 - 15 parts by weight.

8. The bromobutyl rubber composite material according to claim 7, characterized in that: Based on 100 parts by weight of bromobutyl rubber, the addition amount of the organic clay in the composite reinforcing material is 3 - 10 parts by weight.

9. A method for preparing a bromobutyl rubber composite according to any one of claims 1-8, characterized in that, Comprising the following steps: Mixing the bromobutyl rubber solution and the dispersion of the composite reinforcing material evenly, removing the solvent, drying, adding other additives different from the composite reinforcing material, mixing and vulcanizing to obtain the bromobutyl rubber composite material.

10. The preparation method of the bromobutyl rubber composite material according to claim 9, characterized in that: The preparation method of the bromobutyl rubber solution is: Adding bromobutyl rubber into an organic solvent and mixing evenly to obtain a bromobutyl rubber solution.

11. The preparation method of the bromobutyl rubber composite material according to claim 10, characterized in that: The mass concentration of the bromobutyl rubber solution is 10% - 20%; and / or, The organic solvent is an alkane solvent; and / or, The mixing temperature is 10 - 80 °C; and / or, The mixing time is 0.5 - 8 h.

12. The preparation method of the bromobutyl rubber composite material according to claim 11, characterized in that: The organic solvent is n-hexane; and / or, The mixing temperature is 20 - 60 °C; and / or, The mixing time is 1 - 3 h.

13. The preparation method of the bromobutyl rubber composite material according to claim 9, characterized in that: The preparation method of the dispersion of the composite reinforcing material is: Mixing the organic clay and the carrier evenly in an organic solvent.

14. The preparation method of the bromobutyl rubber composite material according to claim 13, characterized in that: The organic solvent is an alkane solvent; and / or, the mass-volume ratio of the organic clay to the organic solvent is (1-15):100; and / or, the temperature of mixing is 10-80°C; and / or, the time of mixing is 0.5-8 h.

15. The preparation method of the brominated butyl rubber composite material according to claim 14, characterized in that: The organic solvent is n-hexane; and / or, the temperature of mixing is 20-60°C; and / or, the time of mixing is 1-6 h.

16. The preparation method of the brominated butyl rubber composite material according to claim 9, wherein: when the brominated butyl rubber solution and the dispersion of the composite reinforcing material are mixed evenly, the temperature of mixing is 10-80°C; and / or, the time of mixing is 0.5-8 h; and / or, the organic solvent is removed by boiling the rubber.

17. The preparation method of the brominated butyl rubber composite material according to claim 16, wherein: when the brominated butyl rubber solution and the dispersion of the composite reinforcing material are mixed evenly, the temperature of mixing is 10-35°C; and / or, the time of mixing is 2-4 h.

18. Application of the brominated butyl rubber composite material according to any one of claims 1-8 or the brominated butyl rubber composite material prepared by the method according to any one of claims 9-17 as an airtight layer material.

19. The application according to claim 18, wherein: the application of the brominated butyl rubber composite material as a tire airtight layer material.