CN113733689B - High-barrier brominated butyl rubber with alternate layered structure and preparation method thereof - Google Patents
High-barrier brominated butyl rubber with alternate layered structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of composite materials, and particularly relates to high-barrier brominated butyl rubber with an alternate layered structure and a preparation method thereof. In the invention, the substrate materials of the layer A and the layer B are all brominated butyl rubber, the brominated butyl rubber can form an integral rubber material after the compression molding process, and the compatibility and the adhesion between the layers are good, so that rich interface energy can be formed, more diffusion paths are provided for gas micromolecules, and further the gas barrier property of the rubber material is improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to high-barrier brominated butyl rubber with an alternate layered structure and a preparation method thereof.
Background
The main functions of the tire inner liner are to prevent gas leakage and to ensure the internal pressure of the tire. During use of aircraft tires, the tires are subjected to high internal pressure, high loads, as well as high temperatures and stresses. The tire inner liner is mostly made of rubber, the mechanical property of the rubber is greatly influenced by temperature, the aging of the rubber can be accelerated, the basic physical and chemical properties of the rubber are changed in a short time due to the aging, and meanwhile, the aviation tire continuously bears periodic alternating stress, so that the tire is easy to flex and fatigue, and the barrier property of the inner liner is influenced.
Therefore, the tire inner liner material is required to have not only high airtightness but also excellent fatigue resistance. The brominated butyl rubber has good gas barrier property and good adhesion with a tire casing material, and is a common material for a tire inner liner.
Patent CN109161110A discloses a tire inner liner rubber added with graphene/carbon black composite material and a preparation method thereof, in the patent, the graphene/carbon black composite material is mechanically stripped to obtain separated graphite slurry and carbon black dispersion liquid, the graphite slurry and the carbon black dispersion liquid are added into butyl bromide rubber, and other fillers, auxiliary materials, auxiliaries and the like are added, and then the inner liner rubber material is obtained by banburying for 3 times. Due to the addition of the graphite slurry and the carbon black dispersion liquid, the dispersibility and the interface compatibility of the graphene and the carbon black in the rubber matrix are improved, the air tightness of the tire is improved, the low gas permeability is kept, the tire pressure is kept in a proper range for a long time, and the service performance of the automobile can be improved in many aspects. However, in the patent, rubber needs to be banburied for many times through co-extrusion mixing, the process is complex, and the production cost is high; on the other hand, during the high-frequency flexing fatigue process of the tire, the air tightness of the tire is seriously reduced by adding the flaky graphene.
Disclosure of Invention
The invention aims to provide high-barrier brominated butyl rubber with an alternate layered structure, which comprises carbon black modified brominated butyl rubber layers and sheet filler modified brominated butyl rubber layers, wherein the two different rubber layers are alternately arranged, the sheet filler modified rubber layers can further improve the air tightness of rubber materials, and the carbon black modified rubber layers can ensure the fatigue resistance of the rubber materials.
The invention is realized by the following technical scheme:
the high-barrier brominated butyl rubber with the alternate layered structure comprises a carbon black modified brominated butyl rubber layer A and a flaky filler modified brominated butyl rubber layer B, wherein the brominated butyl rubber layer A and the brominated butyl rubber layer B are alternately stacked to form the layered brominated butyl rubber, and a two-dimensional flaky filler barrier layer is arranged in the brominated butyl rubber layer B along the direction perpendicular to the gas diffusion direction.
In the invention, the substrate materials of the layer A and the layer B are all brominated butyl rubber, the brominated butyl rubber can form an integral rubber material after the co-vulcanization compression molding process, and the compatibility and the adhesion between the layers are good, so that the mechanical property of the composite material can be further improved.
In the rubber material, a two-dimensional large-size flaky filler barrier layer is arranged in the direction perpendicular to the gas diffusion direction, and the flaky filler is one or more of graphene, graphene oxide, graphite oxide, hydrotalcite, mica sheet, montmorillonite and MXene. The laminated rubber material has large specific surface area and larger diameter-thickness ratio, increases the path for gas to pass through and essentially provides the gas barrier property of the laminated rubber material.
Wherein MXene is two-dimensional transition metal compound, such as two-dimensional transition metal carbide, nitride, carbonitride, boride, etc.
Further, the brominated butyl rubber layer A comprises the following components in parts by weight,
80-100 parts of brominated butyl rubber, 20-80 parts of carbon black, 1-5 parts of zinc oxide, 5-10 parts of naphthenic oil and 0.1-1 part of sulfur.
Further, the brominated butyl rubber layer A comprises the following components in parts by weight,
80-90 parts of brominated butyl rubber, 40-60 parts of carbon black, 3-5 parts of zinc oxide, 5-8 parts of naphthenic oil and 0.3-0.7 part of sulfur.
Further, the brominated butyl rubber layer B comprises brominated butyl rubber, two-dimensional flaky filler, cyclohexane, stearyl trimethyl ammonium halide, zinc oxide, an accelerator and sulfur, wherein the mass ratio of the brominated butyl rubber to the two-dimensional flaky filler is (0.1-8).
In the invention, the dosage of the flaky filler is controlled to be 0.1-8, in the range, the flaky filler barrier layer can be arranged in the rubber in an oriented and ordered way, the barrier effect on gas is best, and simultaneously, the barrier property of the rubber material can be greatly improved only by adding a small amount of flaky filler. When the amount of the added flaky filler is less than 0.1, the barrier layer is sparse and is irregularly arranged; when the content is more than 8, the flaky filler is easy to agglomerate due to more addition amount of the flaky filler, and is not beneficial to the mechanical property and the barrier property of the flaky filler. Under the action of periodic acting force, the barrier layers which are arranged sparsely (less than 0.1) are damaged more easily, so that the arrangement of the original barrier layers is more disordered, and the direction of the barrier layers is changed, thereby reducing the gas barrier property; the more densely arranged barrier layers become more agglomerated under the action of the periodic flexing external force, and holes are generated, so that the gas barrier property and the mechanical property are reduced.
Further, the brominated butyl rubber layer B is characterized in that: the mass ratio of the brominated butyl rubber to the two-dimensional platy filler is preferably 100 (0.1-5).
Further, the brominated butyl rubber layer B is characterized in that: the mass ratio of the brominated butyl rubber to the two-dimensional platy filler is preferably 100 (0.1-3).
Further, the preferred mass ratio of the brominated butyl rubber to the platy filler is 100 (0.1-3). When the addition amount of the graphene is 0.1-3, the graphene barrier layers are arranged most regularly in the rubber, and the barrier layers are arranged most densely and continuously. Under the action of periodic external force, the barrier layers which are continuously arranged can not agglomerate, and each barrier layer can also keep the original arrangement direction, namely, under the action of the external force, the gas barrier property of the rubber material is not greatly changed, and the good gas barrier property is still kept.
Further, the thickness of the alternating layered brominated butyl rubber material is 1-5 mm.
Further, the number of layers of the alternating layered brominated butyl rubber material is 2-256.
Further, the layered brominated butyl rubber has a plurality of brominated butyl rubber layers A and a plurality of brominated butyl rubber layers B.
The invention also aims to provide a preparation method of the high-barrier brominated butyl rubber with the alternating layered structure, which comprises the steps of alternately stacking the brominated butyl rubber layer A and the brominated butyl rubber layer B or alternately stacking and co-extruding the brominated butyl rubber layer A and the brominated butyl rubber layer B by two extruders to obtain a layered brominated butyl rubber material, pressing the layered brominated butyl rubber material for 4 to 10min at room temperature under the pressure of 4 to 20MPa, and vulcanizing the layered brominated butyl rubber material for 0.5 to 3h at the temperature of 100-.
In the invention, two different brominated butyl rubbers are directly laminated and then are pressed and formed in a vulcanizing machine, the forming method is simple, and in the forming process, the orientation arrangement of the sheet-shaped filler barrier layer is kept, so that the barrier layer vertical to the gas diffusion direction is formed in the rubber, and the gas barrier property of the rubber is improved.
Further, the preparation method of the brominated butyl rubber layer A comprises the following steps,
s1, drying the carbon black;
s2, adding the brominated butyl rubber into an open mill, then adding other ingredients such as carbon black and the like, and open milling to obtain the brominated butyl rubber layer A.
Further, the preparation method of the brominated butyl rubber layer B comprises the following steps:
s1 adding cyclohexane into brominated butyl rubber, stirring uniformly at 50-70 ℃, then adding accelerator, zinc oxide and sulfur, and stirring uniformly;
s2, dispersing the two-dimensional flaky filler in water, and performing ultrasonic treatment;
s3 adding stearyl trimethyl ammonium halide into the solution processed in the step S2, stirring uniformly, filtering and washing; dispersing the washed product in water, and performing ultrasonic treatment to obtain a modified flaky filler aqueous solution;
s4, mixing the solution system obtained in the step S1 with the solution system obtained in the step S3, stirring to obtain a water-in-oil emulsion, and freeze-drying to remove cyclohexane and water;
S5, pressing the product of the step S4 after freeze drying at 5-10Mpa and normal temperature for 5-10min to obtain a brominated butyl rubber layer B containing two-dimensional large-size sheet filler.
In the invention, the modified flaky filler solution is used as a water phase, the brominated butyl rubber solution is used as an oil phase, the mixture is stirred for 10-30 minutes at the rotating speed of 400-800rpm to form a stable water-in-oil emulsion, the solvent is removed after freeze drying to construct a three-dimensional large-size hollow spherical shell, in the step S5 press forming process, the hollow spherical shell is oriented directionally, a two-dimensional large-size flaky filler barrier layer is formed in the brominated butyl rubber, the flaky filler barrier layer has a larger length-diameter ratio, and the gas barrier property of the rubber can be provided to a large extent only by adding a small amount of the flaky filler solution.
The technical scheme of the invention at least has the following advantages and beneficial effects:
in the invention, the high-barrier brominated butyl rubber material simultaneously comprises carbon black modified brominated butyl rubber and platy filler modified brominated butyl rubber; the addition of the carbon black modified brominated butyl rubber increases the physical crosslinking points of the brominated butyl rubber, and improves the mechanical property and the fatigue resistance of the brominated butyl rubber material; the sheet filler modified brominated butyl rubber forms a two-dimensional large-size sheet barrier layer in the direction perpendicular to the gas diffusion direction, so that the gas barrier property of the rubber material is improved.
In the invention, the substrate materials of the layer A and the layer B are all brominated butyl rubber, the compatibility and the adhesion between the layers are good, and the periodic flexing action in the use process of the tire enables slippage and shearing to exist between a harder flaky filler region and a softer carbon black region, so that the flaky filler barrier walls at the interface of the layer A and the layer B are arranged more regularly and orderly, thereby reducing the influence of the periodic flexing fatigue action on the gas barrier performance of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a microstructure diagram of a multi-layer rubber material provided in examples 1-4 of the present invention;
FIG. 2 is a graph of storage modulus and loss modulus for multilayer rubber materials provided in examples 5-7 of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Examples
Preparation of carbon Black modified brominated butyl rubber (BIIR/CB):
before the experiment, the carbon black is placed in a drying oven with the temperature of 105 +/-2 ℃ for drying for 2 h. Weighing the materials according to the proportion in the table 1, setting the front and rear roller temperatures of an open mill (LRMR-S-150/W, Laiburtaceae, Thailand) to be 45 ℃ and 35 ℃ respectively, setting the roller speed ratio to be 1.25, placing brominated butyl rubber (BIIR) into the open mill after the open mill is stabilized for 30min to wrap the rollers, sequentially adding small materials into the rollers according to the sequence of zinc oxide, stearic acid, magnesium oxide, carbon black, a tackifier, naphthenic oil, sulfur and an accelerant, cutting the rollers twice respectively after each feeding so as to fully and uniformly mix the components, reducing the roller distance to 0.5mm, wrapping in a triangular shape, rolling for 5 times respectively, and finally adjusting the required roller distance to discharge sheets.
By adopting the preparation method, different BIIR/CB films are prepared according to the raw material proportion in the table 1, and the labels are CB1-CB4 respectively.
TABLE 1 compounding ratio of carbon black-modified brominated butyl rubber
In table 1, each raw material is in terms of added weight portion.
The relevant information of the raw materials used therein is as follows:
brominated butyl rubber (BIIR) having a bromine content of 1.8. + -. 2.2 wt%, brand 2030, Germany, Langshan chemical Co., Ltd;
Carbon Black (CB), designation N550, shanghai cabot chemical limited;
zinc oxide, magnesium oxide, stearic acid, accelerator DM and sulphur, commercially available industrial grade products, Doctorong Chemicals Co.
Naphthenic oils, commercial technical grade products, santa de texae chemical ltd.
Graphene modified brominated butyl rubber (BIIR/mGO):
firstly, 30g of BIIR is put into a 1000ml three-neck flask, 500ml of cyclohexane is added, then the mixture is stirred for 5 hours in a constant temperature water bath at 60 ℃ by a stirrer to obtain a BIIR oil solution, and finally, 0.45g of accelerator DM, 0.9g of zinc oxide and 0.15g of sulfur are added, and the mixture is stirred for 15min to be uniformly dispersed.
Graphite oxide was dispersed in 300ml of deionized water and sonicated for 30min using a cell disruptor (xO-1800D, Nanjing piooho instruments Ltd.), wherein the mass of graphite oxide was 0.3, 0.5, 0.7, 0.9 and 2 wt% with respect to BIIR, respectively. And stripping graphite oxide after ultrasonic treatment to form graphene oxide nanosheets (GO). Adding STAB (octadecyl trimethyl ammonium bromide) with the mass of 30 wt% relative to graphite oxide into the GO aqueous solution, and stirring for 2h in a constant-temperature water bath at 60 ℃ to obtain the STAB grafted GO aqueous solution. Residual STAB was removed by filtration and washing to obtain a modified Pickering emulsifier (mGO). Finally, mGO was dispersed in 300ml of deionized water and sonicated for 30min to give mGO aqueous solution.
The obtained mGO aqueous solution was added to a three-necked flask and mixed with BIIR oil solution, and stirred at 500rpm/min for 12min to form a stable water-in-oil (W/O) Pickering emulsion. When the Pickering emulsion is ready, it is transferred to a freeze dryer as soon as possible. Freeze-drying for 30h removed all cyclohexane and water, and three-dimensional large-size mGO shell structure remained in BIIR. Cold pressing the obtained freeze-dried BIIR at room temperature at 5MPa for 5min, and pressing the three-dimensional mGO hollow shell structure into a two-dimensional large-size mGO nanosheet; finally, vulcanizing at 120 ℃ for 2h to obtain a vulcanized rubber sheet (BmGO) with two-dimensional large-size mGO nanosheet oriented distribution. Brominated butyl rubber films added with 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.9 wt% and 2 wt% of graphene are respectively named as BmGO-0.3, BmGO-0.5, BmGO-0.7, BmGO-0.9 and BmGO-2.0.
Wherein, the used raw material information is as follows:
brominated butyl rubber (BIIR), brand 2030, bromine content 1.8. + -. 2.2 wt.%, Mooney viscosity (ML1+8at 125 ℃) 32. + -.4, Langshan chemical Co., Ltd, Germany;
graphite oxide, sixth element, changzhou, ltd; stearyl trimethylammonium bromide (STAB), commercially available;
cyclohexane, a commercial industrial grade product, metropolis chemicals ltd;
Zinc oxide, accelerator and sulphur, commercially available technical grade products, metropolis chemicals ltd.
Preparing a layered rubber material:
the specific preparation method of examples 3-7 was: pressing the prepared two films to the required thickness according to the requirements of layer thickness and layer number, cutting the films into the required size, alternately laminating the films, pressing the films for 5min at room temperature under the condition of 5MPa by using a flat vulcanizing machine, vulcanizing the films for 2h at 120 ℃ under the condition of 15MPa, and finally preparing the alternate layered composite material with different layer numbers. The preparation methods of examples 1-2 and 8-10 were: cutting the two prepared rubber sheets into long strips, passing through the extrusion flow channels of two extruders, and extrudingMerging the two layers of melt at the position of the co-extrusion die head, dividing the melt into two parts by the layering and overlapping unit, and overlapping the two parts together, so that 2 can be obtained after the melt flows through the n layering and overlapping units (n+1) And pressing the layered sheets of the layers for 5min at room temperature under the condition of 5MPa, and then vulcanizing for 2h at the temperature of 120 ℃ under the condition of 15MPa to finally prepare the alternating layered composite materials with different layers.
The total thickness of the multilayer BIIR rubber composite was 1.5mm, as identified in examples 1-10, respectively.
The number of layers is two, four, six and eight respectively, which are named BIIR-2, BIIR-4, BIIR-6 and BIIIR-8.
The compositions of the corresponding layered rubber materials of examples 1-10 are shown in Table 2. In table 2, the two films are stacked in the same number, that is, the total number of the two films is 4, and the two films include two carbon black modified films and two graphene modified films, and the other embodiments are similar to the above embodiments.
TABLE 2 examples 1-10 compositions of layered rubber materials
In other embodiments of the present invention, the number of layers may also be 10, 12, 14, tens, hundreds, thousands, etc., and the total thickness of the layered rubber material may also be adjusted according to the number of layers.
Comparative examples 1 to 5
As comparative examples 1 to 5, runs 1 to 5 described in the specification of patent CN109161110A were used.
Experimental example:
1. microstructure of layered rubber material
The microstructures of the layered rubber materials of examples 3, 5, 6 and 7 were observed under an optical microscope, and the results are shown in FIG. 1, in which a to d correspond to examples 3, 5, 6 and 7, respectively.
As can be seen in fig. 1, in a-d, the layering of 2, 4, 6, 8 layers is clearly seen. The graphene and carbon black in the composite material are uniformly distributed, the BIIR/CB layers and the BIIR/mGO layers are alternately arranged, and no obvious phase interface exists because the matrix is BIIR. Graphene is in a laminar array and in a lesser amount in BIIR, showing well-ordered laminar barrier walls on the sides of the material.
2. Gas barrier properties of layered rubber materials
The carbon black-modified bromobutyl rubber, the graphene-modified bromobutyl rubber used in example 3, and examples 3, 5, 6, 7 were tested for gas tightness using a VAC-V2 model gas permeameter (denland electromechanical technologies, inc.). The experimental gas is nitrogen, the experimental temperature is 40 ℃, and the testing pressure is 1.5 MPa.
And (3) testing process: uniformly smearing vacuum oil on a non-test area of a cavity, and placing circular filter paper with the diameter of 2cm on the test area; the sample is cut into a 5cm circle and placed in the testing cavity, the upper cavity knob and the lower cavity knob are screwed, the screws are screwed, and the test is started.
In table 3, the permeability coefficient a means a permeability coefficient directly measured without performing aging treatment and fatigue treatment on the rubber material;
the permeability coefficient B refers to the permeability coefficient obtained by aging each sample for 6 hours at 150 ℃ and then measuring;
the permeability coefficient C is a permeability coefficient obtained by performing a flex fatigue test on each sample under the condition that the tensile deformation is 40%, and measuring after 50 ten thousand times of fatigue;
the permeability coefficient D is obtained by aging each sample at 150 ℃ for 6h, performing a flex fatigue test under the condition that the tensile deformation is 40%, and measuring the obtained permeability coefficient after 50 ten thousand times of fatigue; the test is to simulate that in the actual use process of the tire, the temperature of the tire is increased along with the friction action of the tire and the ground besides the periodic fatigue action.
The units of permeability coefficients are all 10 -14 cm 3 ·cm/cm 2 ·s·Pa。
In Table 3, BIIR-CB is the carbon black-modified bromobutyl rubber sheet used in example 3, B mGO-0.7 The graphene modified bromobutyl rubber sheet used in example 3. The BIIR/CB composite rubber system has poor gas barrier property and the permeability coefficient of the BIIR/CB composite rubber system is as high as 1.4 multiplied by 10 -14 cm 3 ·cm/cm 2 s.Pa. In comparison with the former, B mGO-0.7 The rubber sheet has excellent barrier property and small gas permeability coefficient of 0.31 × 10 -14 cm 3 ·cm/cm 2 s.Pa, a 77.9% reduction in the permeability coefficient compared to BIIR/CB films, which is illustrated in B mGO-0.7 The two-dimensional large-size graphene barrier layer perpendicular to the gas passing path effectively reduces the gas passing efficiency, and the system has the advantages. In contrast, the barrier properties of the alternating layered composite decreased with the addition of the BIIR/CB system, but the gas permeability coefficient increased from 1.35X 10 with the number of alternating layers -14 cm 3 ·cm/cm 2 s.Pa down to 0.89X 10 -14 cm 3 ·cm/cm 2 s.Pa. The gas permeability coefficient of BIIR-8 was reduced by 36.4% compared to BIIR/CB rubber, which indicates that the gas barrier properties of BIIR are greatly improved by alternately compounding BIIR/CB layers with BIIR/mGO layers.
After 50 ten thousand dynamic fatigue tests, the permeability coefficient of the gas is measured, and the data in the table 3 can be obtained, after the fatigue tests, the permeability coefficient of the gas is reduced, namely, after 50 ten thousand fatigue actions, the barrier property is improved, which shows that the gas has better fatigue resistance. However, in examples 6 and 7, the gas permeability coefficient decreased less, probably because the number of layers of BIIR-6 and BIIR-8 increased, and the whole possessed better mechanical properties and filler distribution, and the filler distribution changed less after being subjected to fatigue than BIIR-2 and BIIR-4.
After aging for 6h at 150 ℃, the permeability coefficients of BIIR-6 and BIIR-8 are respectively 1.09 multiplied by 10 -14 cm 3 ·cm/cm 2 ·s·Pa、0.89×10 -14 cm 3 ·cm/cm 2 s.Pa down to 0.74X 10 -14 cm 3 ·cm/cm 2 s.Pa and 0.42X 10 -14 cm 3 ·cm/cm 2 s.Pa; after further applying 50 ten thousand times of fatigue action, the permeability coefficient of the material is increased to 1.15 multiplied by 10 - 14 cm 3 ·cm/cm 2 s.Pa and 0.97X 10 -14 cm 3 ·cm/cm 2 s.Pa. That is, there is a significant decrease in the gas barrier properties of BIIR under the combined effects of temperature and fatigue, but the permeability coefficient of the multi-layer BIIR rubber material is still much smaller than that of the BIIR/CB composite rubber system, and still has excellent gas barrier properties.
3. Mechanical properties of layered rubber materials
For the carbon black modified brominated butyl rubber and the graphene modified brominated butyl rubber used in example 3, examples 3, 5, 6 and 7 and comparative examples 1 to 5, the tensile properties of BIIR were tested according to GB/T528-2009 standard by using a microcomputer controlled electronic universal material testing machine (SANS, Shenzhen san Si NZ S.P.S. Co., Ltd.). The sample was cut into a dumbbell-shaped specimen and then conditioned for 3 hours at a temperature of 25 ℃ and a relative humidity of 55%. The adjusted samples were subjected to a tensile test at a rate of 500mm/min, the number of samples per group was 5, and the test results were averaged. The results are shown in Table 3, wherein BIIR-CB is the carbon black-modified brominated butyl rubber sheet used in example 3, B mGO-0.7 The graphene modified bromobutyl rubber sheet used in example 3.
As can be seen from Table 3, BIIR/CB has excellent mechanical properties, with tensile strength and elongation at break of 11.85MPa and 662%, respectively. This is because carbon black can act as a physical crosslinking site in the BIIR, acting to reinforce the crosslinked network of the rubber, thereby giving the BIIR better strength and toughness. Because the reinforcing effect of the graphene is limited and the addition amount is small, B is enabled to be mGO-0.7 The composite material has excellent barrier property and simultaneously sacrifices most of mechanical properties, and the tensile strength and the elongation at break of the composite material are respectively 2.55MPa and 250 percent and are respectively reduced by 78 percent and 62.2 percent.
The mechanical properties of the alternating layers of rubber material BIIR2-8 increased with increasing number of layers. When the number of the alternating layers is increased from 2 to 8, the tensile strength is improved from 3.05MPa to 5.39MPa, and the elongation at break is increased from278% increased to 445% relative to B mGO-0.7 The mechanical property is greatly improved. On the one hand, the two systems have the same base material, so that the two systems have better interface combination; on the other hand, compared with BIIR/CB rubber, the number of the layers of BIIR-8 is more, so that the carbon black filler is distributed in the matrix in a layered mode, the distribution uniformity of the carbon black is increased, and the good reinforcing effect can be achieved. Through the above discussion, it can be found that the barrier property and the mechanical property of the BIIR/CB and BIIR/mGO systems can be well balanced by alternately arranging the BIIR/CB and BIIR/mGO systems in a layered structure, and the barrier property is improved while the use requirement of the mechanical property can be met.
The multi-layer rubbers of examples 5-7 were tested for storage modulus and loss modulus after 50 ten thousand fatigue tests, the results of which are shown in FIG. 2; in FIG. 2, a4-8 represents the storage modulus of the rubber materials of examples 5-7, respectively, and b4-8 represents the loss modulus of the rubber materials of examples 5-7, respectively.
After 50 million fatigue events, the storage modulus at low temperature for BIIR-4, BIIR-6 and BIIR-8 all decreased to some extent compared to the storage modulus without fatigue. With the increase of the number of the layers of the material, the reduction range of the storage modulus after fatigue is gradually reduced, because the carbon black area is more uniformly distributed by the layered compounding, the whole mechanical property of the base material is enhanced. The loss modulus represents the energy loss of the material in the dynamic deformation process caused by asynchronous response between stress and strain when the material is subjected to viscous deformation. BIIR-4, BIIR-6 and BIIR-8 all showed a decrease in loss modulus after fatigue, indicating that the internal friction of BIIR was less, consistent with data obtained by light microscopy. In the fatigue process of the multilayer material, the arrangement of the outer side graphene gradually becomes more regular, so that the loss factor is reduced after the fatigue effect; with the increase of the number of layers of the multilayer material, the number of layer interfaces is increased, the shearing action between the graphene and the carbon black is stronger, the internal friction is increased, and therefore the reduction range of the loss factor is reduced with the increase of the number of layers.
As can be seen from FIG. 2, after 50 ten thousand fatigue events, the storage modulus at low temperature for BIIR-4, BIIR-6 and BIIR-8 all decreased to some extent compared to the non-fatigue state. With the increase of the number of the layers of the material, the reduction range of the storage modulus after fatigue is gradually reduced, because the carbon black area is more uniformly distributed by the layered compounding, the whole mechanical property of the base material is enhanced. The loss modulus represents the energy loss of the material in the dynamic deformation process caused by asynchronous response between stress and strain when the material is subjected to viscous deformation. BIIR-4, BIIR-6 and BIIR-8 all showed a decrease in loss modulus after fatigue, indicating that the internal friction of BIIR was less, consistent with data obtained by light microscopy. In the fatigue process of the multilayer material, the arrangement of the outer side graphene gradually becomes more regular, so that the loss factor is reduced after the fatigue effect; with the increase of the number of layers of the multilayer material, the number of layer interfaces is increased, the shearing action between the graphene and the carbon black is stronger, the internal friction is increased, and therefore the reduction range of the loss factor is reduced with the increase of the number of layers.
4. Fatigue life
The fatigue life of the carbon black-modified bromobutyl rubber, the graphene-modified bromobutyl rubber used in example 3, as well as of examples 3, 5, 6, 7 and comparative examples 1 to 5, was tested according to the provisions and test methods in GB/T1688-. The results are shown in Table 3. Wherein the fatigue life is measured after aging at 150 ℃ for 6h and applying 40% tensile strain during fatigue.
Example 3(BIIR-2), example 5(BIIR-4), example 6(BIIR-6) and example 7(BIIR-8) after aging at 150 ℃ for 6h had an increased fatigue life as the number of alternating layers of BIIR was increased. The fatigue life of BIIR-2 and BIIR-4 is 157 ten thousand times and 178 ten thousand times respectively, BIIR-6 and BIIR-8 are not broken after being fatigued for more than 200 ten thousand times, compared with a BIIR/mGO system, the fatigue life after high temperature action is greatly improved, and the gas barrier property can be well kept while the fatigue action is borne. This shows that the alternating multilayer BIIR still has better fatigue resistance under the thermal aging condition, and embodies the advantages of the alternating layered composite material. The change of the barrier property of the alternating multilayer BIIR mainly has three factors, namely, a crosslinking network for promoting BIIR generation by heat aging is weaker, and the crosslinking network is easily damaged under the action of dynamic fatigue, so that the gas barrier property of a matrix is influenced; secondly, the distribution state of the graphene and the carbon black is changed to a certain extent due to the aging of hot air, and the ordering of the arrangement of the filler is reduced; and thirdly, the graphene regions and the carbon black regions are alternately distributed in the alternate layered composite material, the graphene regions are easily subjected to shearing force parallel to the arrangement direction of the graphene under the action of external force, and the ordered distribution of the two-dimensional graphene barrier walls is promoted, so that the dynamic fatigue action can be improved to a certain extent, and the ordering of the graphene barrier walls can be improved.
But the mechanical properties of the material can be damaged after the hot air aging effect. Thus, for a multilayer BIIR, the barrier properties will be degraded by the combined effects of temperature and fatigue.
TABLE 3 gas Barrier and mechanical Properties of the respective multilayered rubber materials
From Table 3, it can be also seen that the rubber materials of comparative examples 1 to 5 are higher in tensile strength than those of examples 1 to 5, but much worse in gas barrier property than those of examples 1 to 5 and also inferior in fatigue life. As for the tire inner liner layer material, the gas barrier property and the fatigue resistance are key properties, so the rubber materials of the examples 1 to 5 are superior to the rubber materials of the comparative examples 1 to 5, and the rubber material has better mechanical property and gas barrier property under the simultaneous action of high temperature, fatigue and deformation, and is more suitable for being used as the tire inner liner layer material.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A high-barrier brominated butyl rubber with an alternate laminated structure is characterized in that: the rubber layer is characterized by comprising a carbon black modified brominated butyl rubber layer A and a platy filler modified brominated butyl rubber layer B, wherein the brominated butyl rubber layer A and the brominated butyl rubber layer B are alternately stacked to form a layered brominated butyl rubber;
the brominated butyl rubber layer A comprises the following components in parts by weight,
80-100 parts of brominated butyl rubber, 20-80 parts of carbon black, 1-5 parts of zinc oxide, 5-10 parts of naphthenic oil and 0.1-1 part of sulfur;
the brominated butyl rubber layer B comprises brominated butyl rubber, two-dimensional flaky filler, cyclohexane, stearyl trimethyl ammonium halide, zinc oxide, an accelerator and sulfur, wherein the mass ratio of the brominated butyl rubber to the two-dimensional flaky filler is 100 (0.1-8);
the preparation method of the brominated butyl rubber layer A comprises the following steps:
s1, drying the carbon black;
s2, adding the brominated butyl rubber into an open mill, then adding other ingredients of carbon black, and carrying out open milling to obtain a brominated butyl rubber layer A;
the preparation method of the brominated butyl rubber layer B comprises the following steps:
s1 adding cyclohexane into brominated butyl rubber, stirring uniformly at 50-70 ℃, then adding accelerator, zinc oxide and sulfur, and stirring uniformly;
S2, dispersing the two-dimensional flaky filler in water, and carrying out ultrasonic treatment;
s3 adding stearyl trimethyl ammonium halide into the solution processed in the step S2, stirring uniformly, filtering and washing; dispersing the washed product in water, and performing ultrasonic treatment to obtain a modified flaky filler aqueous solution;
s4, mixing the solution system obtained in the step S1 with the solution system obtained in the step S3, stirring to obtain a water-in-oil emulsion, and freeze-drying to remove cyclohexane and water;
s5, pressing the product of the step S4 after freeze drying at 5-10Mpa and normal temperature for 5-10min to obtain a brominated butyl rubber layer B containing two-dimensional large-size sheet filler.
2. The alternating layered high barrier bromobutyl rubber of claim 1 wherein: the flaky filler is one or more of graphene, graphene oxide, graphite oxide, hydrotalcite, mica sheet, montmorillonite and MXene.
3. The alternating layered high barrier bromobutyl rubber of claim 1 wherein: the brominated butyl rubber layer A comprises the following components in parts by weight,
80-90 parts of brominated butyl rubber, 40-60 parts of carbon black, 3-5 parts of zinc oxide, 5-8 parts of naphthenic oil and 0.3-0.7 part of sulfur.
4. The alternating layered high barrier bromobutyl rubber of claim 1 wherein: the mass ratio of the brominated butyl rubber to the two-dimensional flaky filler is 100 (0.1-5).
5. The high barrier bromobutyl rubber of alternating layer structure according to claim 1, characterized in that: the thickness of the layered brominated butyl rubber is 1-5 mm.
6. The high barrier bromobutyl rubber of alternating layer structure according to claim 1, characterized in that: the number of layers of the layered brominated butyl rubber is 2-256.
7. A process for preparing a high barrier bromobutyl rubber of alternating layer structure as claimed in any of claims 1 to 6, characterized in that: comprises alternately stacking the brominated butyl rubber layer A and the brominated butyl rubber layer B or alternately stacking and co-extruding the brominated butyl rubber layer A and the brominated butyl rubber layer B by two extruders to obtain the layered brominated butyl rubber, pressing the layered brominated butyl rubber for 4 to 10min at the room temperature under the condition of 4 to 20MPa, and vulcanizing the layered brominated butyl rubber for 0.5 to 3h at the temperature of 100 ℃ and 140 ℃ under the condition of 4 to 20 MPa.
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| CN109161110A (en) * | 2018-08-17 | 2019-01-08 | 厦门凯纳石墨烯技术股份有限公司 | A kind of addition graphene/carbon black composite material tyre airtight layer glue and preparation method thereof |
| CN110240763A (en) * | 2019-05-23 | 2019-09-17 | 大连工业大学 | A kind of wet process prepares bromine buna/polyethylene barrier property functional composite membrane method |
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| CN107815031A (en) * | 2017-12-27 | 2018-03-20 | 双钱集团（江苏）轮胎有限公司 | A kind of Recipe of the inner liner containing brombutyl natural rubber |
| CN109161110A (en) * | 2018-08-17 | 2019-01-08 | 厦门凯纳石墨烯技术股份有限公司 | A kind of addition graphene/carbon black composite material tyre airtight layer glue and preparation method thereof |
| CN110240763A (en) * | 2019-05-23 | 2019-09-17 | 大连工业大学 | A kind of wet process prepares bromine buna/polyethylene barrier property functional composite membrane method |
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