Method for producing rubber material for hoses and hose

Abstract

The application discloses a rubber material preparation method for rubber tubes and a rubber tube. The rubber material preparation method for rubber tubes comprises the following steps: mixing a foaming agent, a rubber matrix, an additive and a first carbon material to form a mixed product; preparing the mixed product into a foaming product by using a microwave process; adhering, compounding or laminating two parts of at least one pair of specific surfaces or two parts of one circle of surfaces of the foaming product with two layers of unvulcanized or incompletely vulcanized rubber to form a composite rubber; and vulcanizing the composite rubber by using a vulcanization process to form the rubber material for rubber tubes. The application can prepare the rubber material for rubber tubes which has good bending performance and better interface combination between a buoyancy layer and other rubber layers.

Description

Technical Field

[0001] This application relates to the field of rubber technology, and more specifically, to a method for preparing rubber materials for hoses and hoses, particularly to marine engineering hoses. Background Technology

[0002] Existing marine engineering hoses, especially those suitable for deep-sea engineering, are typically made of low-density materials to facilitate suspension or floating in water. These low-density materials are often composite materials, such as those formed by sandwiching a buoyancy layer material between two rubber layers.

[0003] However, since the buoyancy layer material used is usually made of resin as a matrix through foaming, it is typically hard and brittle, and has poor bending performance, making it difficult to achieve winding, storage, and transportation, thus limiting its application. Furthermore, because the buoyancy layer matrix is ​​resin, the hoses manufactured using the sandwich method have a significant phase interface, which becomes a major problem restricting the application of such hoses. In addition, since the resin layer and rubber layer in these hoses are usually bonded by hard adhesive, there is a significant difference in modulus between the two layers, significantly limiting their application in bending and other aspects. For example, after repeated bending, the resin and rubber may delaminate, leading to a decrease in hose performance. Moreover, because the resin layer is hard, brittle, and lacks flexibility, the cells in the resin layer are hard cells with poor pressure and bending resistance. Therefore, during repeated use, defects such as internal fractures can easily occur in the resin layer, causing the cells to connect and form through-holes.

[0004] Furthermore, the processing of such marine engineering hoses typically requires at least two stages of vulcanization: first, the inner rubber layer wrapped with buoyancy layer material is vulcanized; then, the buoyancy layer material is wrapped around the inner rubber layer; then, the outer rubber layer is wrapped around the inner rubber layer; and finally, the outer rubber layer is vulcanized to form the final rubber material for the hose. This makes the manufacturing process of the rubber material for hoses quite complex.

[0005] Therefore, a new technical solution is needed to prepare rubber materials for hoses that have better bending performance and better interfacial bonding between the buoyancy layer and other rubber layers. Summary of the Invention

[0006] One objective of this application is to provide a method for preparing rubber materials for hoses and a new technical solution for hoses.

[0007] According to a first aspect of this application, a method for preparing a rubber material for hoses is provided, comprising: The foaming agent, rubber matrix, additives and first carbon material are mixed to form a compound; The mixture was prepared into a foamed product using a microwave process. The foamed product is bonded, laminated, or stacked with two layers of unvulcanized or incompletely vulcanized rubber to form a composite rubber. The composite rubber is vulcanized using a vulcanization process to form a rubber material for hoses. Wherein, the first carbon material is a carbon material containing a graphene structure; the pair of specific surfaces are two opposing surfaces; the two parts of the ring surface are two opposing parts; and the temperature of either the pair of specific surfaces or the two parts of the ring surface is lower than the vulcanization temperature of the foamed product before and after microwave processing, or either the pair of specific surfaces or the two parts of the ring surface is not vulcanized or not fully vulcanized.

[0008] Preferably, the first carbon material includes at least one of graphene, graphene oxide, graphite, and expandable carbon material; Wherein, the graphene is single-layer graphene, multi-layer graphene, or stacked graphene; the graphene oxide is single-layer graphene oxide, multi-layer graphene oxide, or stacked graphene oxide; the expandable carbon material includes unexpanded expandable graphite, foaming agent intercalated graphite, graphene, or graphene oxide. Furthermore, when the first carbon material includes the expandable carbon material, the expandable carbon material is also considered as a type of foaming agent.

[0009] Preferably, when the foaming agent is not a carbon material, the vaporization or decomposition temperature of the foaming agent is less than or equal to 300°C; And / or, when the first carbon material contains expandable carbon material, the foaming agent vaporizes or decomposes to generate gas at a first temperature; wherein, the first temperature is the temperature at which the expandable carbon material loses 30% of its mass under an inert gas atmosphere.

[0010] Preferably, the mass ratio of the foaming agent to the rubber matrix is ​​3~80:100; Furthermore, the mass ratio of the first carbon material to the rubber matrix is ​​1~80:100.

[0011] Preferably, the mixture of foaming agent, rubber matrix, additives and first carbon material to form a compound includes: A continuous extrusion process is used to mix foaming agent, rubber matrix, additives and first carbon material to form a compound, and the compound is continuously discharged in the form of strips, plates, strips, rods or hollow tubes. Alternatively, the foaming agent, rubber matrix, additives and first carbon material are mixed to form a compound, and the compound is cut and / or spliced ​​to form a strip, plate, strip, rod or hollow tubular compound.

[0012] Preferably, the preparation of the foamed product from the compound using a microwave process includes: The ratio of the power of microwave radiation received by the compound to the mass of the rubber matrix and the first carbon material is greater than or equal to 40 W / g. And / or, the heating rate of the first carbon material is greater than or equal to 10 °C / s; And / or, the heating rate of the rubber matrix in the region adjacent to the first carbon material is greater than or equal to 10°C / s.

[0013] Preferably, the preparation of the foamed product from the compound using a microwave process includes: The continuous extrusion process is combined with microwave processing to form foamed products in the form of strips, plates, strips, rods or hollow tubes. Alternatively, microwave processes can be used to prepare foamed products from strip-shaped, plate-shaped, strip-shaped, rod-shaped, or hollow tubular mixtures.

[0014] Preferably, the preparation of the foamed product from the compound using a microwave process includes: The mixture is treated with constant microwave power, or with gradually varying microwave power, or with at least two intermittently applied microwaves. Among them, the power of two adjacent microwave segments may be the same or different.

[0015] Preferably, bonding, laminating, or stacking at least one pair of specific surfaces or two portions of a ring of the foamed product with two layers of uncured or incompletely cured rubber to form a composite rubber includes: After wrapping and bonding one of the two parts of the pair of specific surfaces or a ring of surfaces to the surface of an unvulcanized or incompletely vulcanized rubber, another unvulcanized or incompletely vulcanized rubber is then bonded, wrapped, or stacked on the other surface or part of the pair of specific surfaces or a ring of surfaces to form a laminated composite rubber.

[0016] Preferably, the composite rubber is vulcanized using a vulcanization process to form a rubber material for hoses, comprising: During the vulcanization process of the composite rubber, microwave technology is used to assist in heating the composite rubber to form a rubber material for hoses. In this embodiment, at least one of the two layers of uncured or incompletely cured rubber includes a second carbon material, which is a carbon material containing a graphene structure.

[0017] Preferably, the preparation of the foamed product from the compound using a microwave process includes: The mixture is microwave-processed after at least one pair of specific surfaces are placed in a mold or fixed by a fixture, and the temperature of the surface of the mold or fixture in contact with at least one pair of specific surfaces of the mixture is lower than the vulcanization temperature of the mixture before and after the mixture is prepared into a foamed product by microwave process.

[0018] According to a second aspect of this application, a rubber hose is provided, wherein the rubber hose is prepared using a rubber material for rubber hose prepared by the method for preparing rubber material for rubber hose as described in any one of the first aspects.

[0019] The method for preparing rubber materials for hoses in this application involves first mixing a foaming agent, a rubber matrix, additives, and a first carbon material to form a compound. Then, the first carbon material in the compound is heated using a microwave process, causing some or all of the foaming agent in the compound to quickly reach the foaming temperature to form a foamed product. Simultaneously, due to the low absorption of microwaves by the rubber matrix, the rubber matrix will be in an unvulcanized or incompletely vulcanized state below the vulcanization temperature during this process. That is, by asynchronously carrying out rubber foaming and rubber vulcanization, the foamed product, especially at least one pair of specific surfaces or two parts of a ring of surfaces of the foamed product, can be in an unvulcanized or incompletely vulcanized state. This facilitates the bonding, lamination, or stacking of the foamed product with two layers of unvulcanized or incompletely vulcanized rubber to form a composite rubber. Then, a co-vulcanization process is used to form a rubber material for hoses with good bending performance and better interfacial bonding between the buoyancy layer and other rubber layers.

[0020] Other features and advantages of this application will become clear from the following detailed description of exemplary embodiments of this application with reference to the accompanying drawings. Attached Figure Description

[0021] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments of the present application and, together with their description, serve to explain the principles of the present application.

[0022] Figure 1 This is a flowchart of a method for preparing rubber material for hoses in one embodiment of this application.

[0023] Figure 2 This is a schematic diagram of the structure of a method for preparing rubber material for hoses in one embodiment of this application. Figure 1 .

[0024] Figure 3This is a schematic diagram of the structure of a method for preparing rubber material for hoses in one embodiment of this application. Figure 2 .

[0025] Figure 4 This is a schematic diagram of the structure of a method for preparing rubber material for hoses in one embodiment of this application. Figure 3 .

[0026] Figure 5 This is a schematic diagram of the structure of the rubber material for the hose in one embodiment of this application.

[0027] Figure 6 This is a cross-sectional view of the rubber material used for hoses in Embodiment 1 of this application.

[0028] Figure 7 This is a cross-sectional view of the rubber material used for hoses in Embodiment 2 of this application.

[0029] Explanation of reference numerals in the attached figures: 1. Mixing apparatus; 2. Mixture; 3. Conveying device; 4. Microwave; 5. Foamed product; 51. A pair of specific surfaces; 6. Uncured or incompletely cured rubber; 7. Inner layer rubber; 8. Outer layer rubber. Detailed Implementation

[0030] Various exemplary embodiments of the present application will now be described in detail with reference to the accompanying drawings. It should be noted that, unless otherwise specifically stated, the relative arrangement, numerical expressions, and values ​​of the components and steps set forth in these embodiments do not limit the scope of the present application.

[0031] The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the scope of this application and its application or use.

[0032] Techniques, methods, and equipment known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques, methods, and equipment should be considered part of the specification.

[0033] In all the examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values.

[0034] like Figure 1 As shown, the method for preparing rubber material for hoses in this application includes the following steps S101~S104: S101, the foaming agent, rubber matrix, additives and first carbon material are mixed to form compound 2; It should be noted that, in this embodiment, by mixing the foaming agent, rubber matrix, additives, and first carbon material, the first carbon material in the mixture 2 can absorb microwaves 4 and form local hot spots when the mixture 2 is prepared into foamed product 5 using microwave technology. The temperature of these hot spots can cause the foaming agent in the vicinity of the first carbon material to foam (wherein, when the first carbon material is an expandable carbon material, it will also foam itself). At the same time, since the rubber matrix has a weak microwave absorption capacity of 4, the rubber matrix will not heat up rapidly due to the absorption of microwaves 4, so that the rubber matrix as a whole is still below the vulcanization temperature of the rubber, which facilitates the asynchronous occurrence of rubber foaming and rubber vulcanization.

[0035] Among them, such as Figure 2 and Figure 4 As shown, in order to improve the preparation efficiency of compound 2, it is preferable to use a mixing device 1 to mix the foaming agent, rubber matrix, additives and first carbon material to form compound 2.

[0036] In one embodiment, the foaming agent includes at least one selected from AC foaming agent, paraffin wax, cyclohexane, butyl acetate, and paraffin oil.

[0037] Specifically, in the embodiments of this application, a single foaming agent or multiple foaming agents can be selected according to the actual needs of the hose. For example, any single foaming agent selected from AC foaming agent, paraffin wax, cyclohexane, butyl acetate, and paraffin oil can be used to improve the foaming stability of the mixture 2; or a combination of any two or more foaming agents selected from AC foaming agent, paraffin wax, cyclohexane, butyl acetate, and paraffin oil can be used to adjust the foaming speed of the mixture 2 and improve the quality of the foamed product 5. Those skilled in the art can make selections according to actual needs, and this application does not impose specific limitations here.

[0038] In one embodiment, the rubber matrix includes at least one of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, ethylene propylene diene monomer (EPDM) rubber, and silicone rubber.

[0039] Specifically, in the embodiments of this application, a single rubber matrix can be selected according to the actual needs of the rubber hose, such as any one of natural rubber, styrene-butadiene rubber, butadiene rubber, ethylene propylene diene monomer (EPDM) rubber, or silicone rubber; or it can be a blended rubber formed by mixing any two or more of natural rubber, styrene-butadiene rubber, butadiene rubber, EPDM rubber, and silicone rubber in any proportion. Those skilled in the art can make the selection according to actual needs, and this application does not impose specific restrictions here.

[0040] In one embodiment, the additives include a vulcanizing agent and a vulcanization accelerator.

[0041] Specifically, in this embodiment of the application, a vulcanizing agent and a vulcanization accelerator are added to the compound 2 to facilitate the subsequent vulcanization process of the foamed product 5 into rubber material for rubber hoses.

[0042] For example, when the foaming agent is AC foaming agent, the rubber matrix is ​​natural rubber, the additives are vulcanizing agent and vulcanization accelerator, and the first carbon material is graphene, the graphene, heated by absorbing microwaves, can raise the temperature of the natural rubber in the adjacent area. This causes the AC foaming agent in this adjacent area to decompose and foam. The decomposed gas will generate bubbles in the natural rubber in this area, and the heated natural rubber will have a lower viscosity, which is conducive to the formation of bubbles and the initiation of the vulcanization process in this area. Then, the microwave heating process can be stopped, or stopped after a short period of microwave heating. During this process, the already formed heating area will maintain a high temperature for a certain period of time, so the vulcanization process in this area will continue, and the bubbles will at least maintain their volume. As the vulcanization process continues, the natural rubber around the bubbles is gradually vulcanized and formed, and then a vulcanized wall with a certain strength is formed inside the foamed product 5 from the interface between the bubbles and the natural rubber. During the subsequent cooling or heating of the rubber material for the hose, the vulcanized wall can further prevent the expansion or closure of the bubbles, thereby ensuring the strength and integrity of the pores, that is, ensuring that the foamed product 5 has a low density.

[0043] In some embodiments, since the vulcanized wall should be formed at least after the foaming agent has foamed to form cells, or the vulcanized wall is still in the scorching or hot vulcanization stage when the cells are formed, it is generally difficult to form the desired cells if the vulcanization of the foamed product 5 is faster than the formation of cells.

[0044] Therefore, in order for the vulcanization accelerator to have a relatively slow vulcanization speed, the vulcanization accelerator preferably includes at least one of thiazole vulcanization accelerators, sulfenamide vulcanization accelerators, guanidine vulcanization accelerators, aldehyde-amine vulcanization accelerators, and thiourea vulcanization accelerators. For example, the vulcanization accelerator may include at least one of accelerator TT, accelerator CZ, accelerator H, accelerator DPG, accelerator DM, and accelerator DOTG.

[0045] In one embodiment, the first carbon material includes at least one of graphene, graphene oxide, graphite, and expandable carbon material; wherein the graphene is single-layer graphene, multi-layer graphene, or stacked graphene; the graphene oxide is single-layer graphene oxide, multi-layer graphene oxide, or stacked graphene oxide; the expandable carbon material includes unexpanded expandable graphite, foaming agent-intercalated graphite, graphene, or graphene oxide; and when the first carbon material includes expandable carbon material, the expandable carbon material is also considered as a foaming agent.

[0046] Specifically, in this embodiment of the application, by adding at least one of graphene, graphene oxide, graphite and expandable carbon material to the compound 2, the excellent microwave absorption and heating characteristics of the first carbon material can be used to adapt to various rubber materials for hoses with different performance requirements, thereby further improving the applicability of rubber materials for hoses.

[0047] In some embodiments, since expandable carbon materials include unexpandable graphite, graphite intercalated with a foaming agent, graphene, or graphene oxide, and since unexpandable graphite, graphite intercalated with a foaming agent, graphene, or graphene oxide can expand and foam, some components of the foaming agent can also be expandable carbon materials, i.e., expandable carbon materials are also considered a type of foaming agent. Thus, by using this first carbon material that combines microwave absorption and heating characteristics with foaming function, the complexity of materials required for production is reduced, while the synergy between microwave absorption and heating of the first carbon material and foaming by the foaming agent is improved, the foaming effect of the foamed product 5 is optimized, and the preparation quality of the foamed product 5 is improved.

[0048] In one embodiment, when the foaming agent is not a carbon material, the temperature of the gas produced by the vaporization or decomposition of the foaming agent is less than or equal to 300°C.

[0049] Specifically, if the temperature of the gas produced by the vaporization or decomposition of the foaming agent exceeds 300°C, the excessively high foaming or decomposition temperature will also require the first carbon material to be heated to such an excessively high temperature. That is, this will cause the rubber matrix containing the foaming agent adjacent to the first carbon material to reach such a high temperature. On the one hand, this may cause the rubber matrix to vulcanize more quickly, resulting in vulcanization being significantly faster than foaming, making it difficult to form the desired cells; on the other hand, it may cause the rubber matrix to carbonize due to the excessively high temperature. Carbonized rubber will be difficult to form cells, resulting in the foamed product 5 not having the desired bending properties, or even failing to form a foamed product.

[0050] In this embodiment, by controlling the vaporization or decomposition temperature of the foaming agent to 300°C or below, it is possible to ensure that the foaming agent generates bubbles in a timely manner under the rapid heating of microwave 4, thereby improving the foaming efficiency of the compound 2. On the other hand, it is also possible to avoid problems such as premature vulcanization of the rubber matrix caused by excessively high temperature, which is conducive to forming a foamed product 5 with uniform structure and stable performance.

[0051] In addition, it should be noted that the foaming agent needs to generate bubbles during the decomposition process in order to improve the foaming efficiency of compound 2.

[0052] In one embodiment, when the first carbon material contains expandable carbon material, the foaming agent vaporizes or decomposes at a first temperature; wherein the first temperature is the temperature at which the expandable carbon material loses 30% of its mass under an inert gas atmosphere.

[0053] Specifically, since the first carbon material usually has a higher density than the rubber matrix, when an expandable carbon material is used, in order for the expandable carbon material to provide sufficiently large pores to facilitate the preparation of the buoyancy layer material required for marine engineering pipes, the expandable carbon material used needs to be able to lose at least 30% of its mass due to heat. That is, preferably when the first carbon material contains expandable carbon material, the foaming agent vaporizes or decomposes at the first temperature.

[0054] In this embodiment of the application, foamed product 5 is prepared by using expandable carbon material. That is, the first carbon material includes expandable carbon material, which is also a type of foaming agent. At this time, the first temperature of the other foaming agents contained in the foaming agent is the temperature at which the expandable carbon material loses 30% of its mass under an inert gas atmosphere.

[0055] Therefore, by setting the vaporization or decomposition temperature of the foaming agent to the temperature corresponding to a 30% mass loss of the expandable carbon material under an inert gas atmosphere, the actual heating behavior of the first carbon material in the microwave field 4 can be more accurately matched, reducing energy consumption. That is, by limiting the vaporization or decomposition temperature of the foaming agent, this embodiment of the application can ensure that the foaming agent is effectively triggered by the local hot spots formed by the first carbon material during microwave heating 4, thereby completing foaming quickly and uniformly. At the same time, it avoids premature complete vulcanization of the rubber matrix due to excessively high foaming temperature, ensuring that the foamed product 5 can be at least partially incompletely vulcanized, which facilitates the subsequent vulcanization process to prepare the foamed product 5 into rubber material for hoses.

[0056] In addition, it should be noted that the first temperature is the temperature at which the expandable carbon material loses 30% of its mass under inert gas atmosphere conditions.

[0057] In one embodiment, the mass ratio of the foaming agent to the rubber matrix is ​​3 to 80:100; and the mass ratio of the first carbon material to the rubber matrix is ​​1 to 80:100.

[0058] Specifically, when a foaming agent with a mass ratio exceeding 80:100 is added, it will result in excessive pores in the final foamed product 5, and will also result in poor bending performance of the foamed product 5. When the amount of foaming agent added is too small, it is not enough to generate enough pores, so that the density of the hose cannot be reduced to the low density required for marine engineering hoses. Therefore, in order to make the hose have a reduced density to adapt to marine engineering applications, the mass ratio of foaming agent to rubber matrix is ​​preferably 3 to 80:100 in this embodiment of the application.

[0059] In some embodiments, the mass ratio of foaming agent to rubber matrix can also be 3 to 30:100, such as 10:100, 20:100 or 30:100.

[0060] Furthermore, excessive addition of the first carbon material not only leads to too many hot spots in the compound 2, requiring precise control during the microwave process, but also causes the rubber compound in the first carbon material to rapidly rise above the vulcanization temperature due to microwave heating 4, resulting in simultaneous rubber foaming and vulcanization. Excessive addition of the first carbon material also significantly reduces the bending performance of the prepared rubber compound, making it hard and brittle, thus hindering its application in marine engineering. Conversely, insufficient addition of the first carbon material makes it difficult for the compound 2 to form enough local hot spots, preventing the foaming agent from foaming. Therefore, in order to prepare a rubber hose material with good bending performance and better interfacial bonding between the foamed rubber 5 (buoyancy layer) and other rubber layers, the preferred mass ratio of the first carbon material to the rubber matrix is ​​1~80:100.

[0061] In one embodiment, the first carbon material includes an expandable carbon material, and the foam product 5 contains pores having all or part of pore walls formed of a non-rubber material.

[0062] Specifically, based on the premise that the first carbon material includes expandable carbon materials, unexpectedly, when expandable carbon materials are used as the first carbon material, such as unexpanded expandable graphite, since unexpanded expandable graphite can also foam, it can be heated and expanded under the action of microwaves 4 to form cells, and at the same time, non-rubber cell walls with structures such as graphene are generated, i.e., solid bubbles are generated. Thus, since such graphene-structured cell walls not only support the cells but also act as a heat source, they can also heat the adjacent rubber matrix, promote the vulcanization of the rubber matrix, and form a barrier to prevent gas from passing through its surface, which is beneficial to maintaining the cells. In addition, when expandable carbon materials such as unexpanded expandable graphite are not used as foaming agents, such as cyclohexane or AC foaming agents, these foaming agents vaporize (such as cyclohexane) or decompose (AC foaming agent) when heated to produce gas. The foamed product forms hollow bubbles without walls, meaning the pores are enclosed by the rubber matrix. This means that the pores rely entirely on the curing and shaping of the rubber matrix after vulcanization to maintain their shape. Therefore, more precise temperature control is required during the foaming process. If vulcanization and shaping are not carried out in time, such as when cyclohexane condenses due to cooling, the pores will shrink. At the same time, there is a higher probability that the gas will dissolve significantly in the rubber, causing gas escape. Even if negative pressure is generated inside the pores, the pores will collapse. Such wallless pores will also have significantly low storage stability. The resulting foamed product will need to be vulcanized within a short period of time (e.g., 1 month, 1 week, or even 1 day) to achieve pore stability. Therefore, in order to ensure the storage stability of the foamed product 5 and facilitate the formation of a relatively long-term foamed product 5, preferably, the first carbon material is an expandable carbon material, and the mass ratio of such expandable carbon material to the rubber matrix is ​​5~15:100.

[0063] In one embodiment, mixing the foaming agent, rubber matrix, additives and first carbon material to form compound 2 includes: using a continuous extrusion process to mix the foaming agent, rubber matrix, additives and first carbon material to form compound 2, and continuously discharging compound 2 in the form of strips, plates, strips, rods or hollow tubes.

[0064] Specifically, since marine engineering pipes are typically layered to form multi-wall structures, in order to facilitate the bonding, lamination, or stacking of at least one pair of specific surfaces 51 of the foamed product 5 with two layers of uncured or incompletely cured rubber 6, the foamed product 5 can be applied to the surface of the inner rubber layer 7 of the hose in a layer-by-layer winding manner and further cured and molded through co-curing, such as... Figure 2 and Figure 4 As shown, a continuous extrusion process is preferably used to mix the foaming agent, rubber matrix, additives and first carbon material to form compound 2, and the compound 2 is continuously discharged in the form of strips, plates, strips, rods or hollow tubes to improve the preparation efficiency of rubber materials for hoses.

[0065] In some embodiments, in order to facilitate the bonding, lamination or stacking of two parts of the surface of the foamed product 5 with two layers of unvulcanized or incompletely vulcanized rubber 6, a continuous extrusion process can be used to mix the foaming agent, rubber matrix, additives and first carbon material to form a compound 2, and the compound 2 can be continuously discharged in the form of strips, plates, strips, rods or hollow tubes.

[0066] In one embodiment, mixing the foaming agent, rubber matrix, additives and first carbon material to form a compound 2 includes: mixing the foaming agent, rubber matrix, additives and first carbon material to form a compound 2, and cutting and / or splicing the compound 2 to form a strip, plate, strip, rod or hollow tube compound.

[0067] Specifically, since marine engineering pipes are usually stacked in a layered winding manner to form a multi-layered wall structure, in order to facilitate the bonding, compounding or stacking of at least one pair of specific surfaces 51 of the foamed product 5 with two layers of uncured or incompletely cured rubber 6, so that the foamed product 5 can be covered on the surface of the inner rubber layer 7 of the rubber material for hoses in a layered winding manner, and further vulcanized by co-curing, it is preferable to mix the foaming agent, rubber matrix, additives and first carbon material to form a compound 2, and cut and / or splice the compound 2 to form a strip, plate, strip, rod or hollow tubular compound, thereby improving the preparation efficiency of the rubber material for hoses.

[0068] In some embodiments, in order to facilitate the bonding, lamination or stacking of two portions of the surface of the foamed product 5 with two layers of unvulcanized or incompletely vulcanized rubber 6, the foaming agent, rubber matrix, additives and first carbon material can be mixed to form a compound 2, and the compound 2 can be cut and / or spliced ​​to form strips, plates, strips, rods or hollow tubes.

[0069] S102, the mixture 2 is prepared into foamed product 5 using microwave technology; It should be noted that, since the foaming of rubber needs to precede the vulcanization of rubber, so that after obtaining the foamed product 5, the obtained foamed product 5 still retains an unvulcanized or incompletely vulcanized surface, and allows heat to be transferred more from the inside of the rubber to the outer surface of the rubber, rather than from the outer surface of the rubber to the inside of the rubber, it is preferable to use microwave technology to heat the compound 2 to prepare the compound 2 into the foamed product 5.

[0070] Among them, because the rubber matrix has poor ability to heat up due to microwave absorption, the compound 2 is difficult to heat up quickly to the temperature required for foaming by the foaming agent under microwave irradiation 4, which makes it easy for rubber foaming and rubber vulcanization to occur simultaneously.

[0071] Therefore, to solve the above problems, it is preferable to add a first carbon material to the compound 2. The first carbon material has a significantly stronger ability to absorb microwaves 4 and generate heat than the rubber matrix, allowing it to absorb microwaves 4 and form localized hot spots. Consequently, the temperature of these hot spots enables the first carbon material itself and the foaming agent in the adjacent area to foam, and since the rubber matrix has a weaker microwave absorption capacity, the rubber matrix will not absorb microwaves 4 and heat up rapidly.

[0072] That is, through the above process, the rubber matrix as a whole is still below the vulcanization temperature of rubber, so that the compound 2 is finally prepared into an unvulcanized or incompletely vulcanized foamed product 5, that is, the separation of rubber foaming and rubber vulcanization steps is achieved.

[0073] In addition, in order to ensure that the first carbon material can absorb microwaves 4 and form local hot spots, the first carbon material is preferably a carbon material containing a graphene structure, that is, the first carbon material includes at least one of graphene, graphene oxide, graphite and expandable carbon materials.

[0074] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: the ratio of the power of the microwave 4 irradiation received by the compound 2 to the mass of the rubber matrix and the first carbon material is greater than or equal to 40 W / g.

[0075] Specifically, when the mixture 2 is prepared into foamed product 5 using microwave technology, the first carbon material in the mixture 2 can absorb microwave 4 and form local hot spots. The temperature of these hot spots can cause the first carbon material itself and the foaming agent in the adjacent area to foam. At the same time, since the rubber matrix has a weak microwave 4 absorption capacity, the rubber matrix will not absorb microwave 4 and heat up rapidly. Even so, the rubber matrix as a whole is still below the vulcanization temperature of rubber, thus ultimately forming an unvulcanized or incompletely vulcanized foamed product 5.

[0076] However, because the rubber matrix has a relatively lower microwave absorption and heat generation capacity compared to the first carbon material, on the one hand, when heated with a lower microwave power, for a given mass of compound 2, especially for a given mass of compound 2 formed by the rubber matrix and the first carbon material, the microwave absorption capacity of the rubber matrix will have a shielding effect on the first carbon material, resulting in a reduction in the microwave power that the first carbon material can absorb. This will make it difficult for the first carbon material to heat up to the temperature required for foaming and expansion of itself and the foaming agent in the adjacent area in a short time, resulting in a longer microwave heating time. On the other hand, a longer microwave heating time will also easily cause the rubber matrix to gradually heat up to a higher temperature under the combined effect of microwave absorption and heat generation and heat conduction, so that the rubber matrix far from the first carbon material will also heat up sufficiently, resulting in a lack of significant temperature difference between the rubber matrix area far from the first carbon material and the first carbon material. Furthermore, when the temperature of the first carbon material and its adjacent area rises to a level sufficient to cause the foaming agent to foam, the temperature of other areas is also likely to rise to a level far exceeding the vulcanization temperature of the rubber matrix, resulting in complete vulcanization of the rubber matrix, which is not conducive to the asynchronous process of rubber foaming and rubber vulcanization.

[0077] Therefore, in order to solve the above problems, it is preferable that the power of microwave radiation 4 received by the compound 2 is greater than or equal to the mass of the rubber matrix and the first carbon material, so as to enable the first carbon material and the rubber matrix in the adjacent area to achieve a heating rate of more than 10°C / s, thereby forming a significant temperature difference in the compound 2, so that the foamed product 5 has unvulcanized or incompletely vulcanized parts or surfaces.

[0078] Of course, in order to ensure the efficiency and quality of the preparation of foamed product 5, the ratio of the power of microwave radiation 4 received by the compound 2 to the mass of the rubber matrix and the first carbon material can be greater than or equal to 80W / g, or the ratio of the power of microwave radiation 4 received by the compound 2 to the mass of the rubber matrix and the first carbon material can be greater than or equal to 100W / g.

[0079] In some embodiments, to create a significant temperature gradient between the rubber matrix and the first carbon material regions, facilitating the separation of the rubber foaming and vulcanization steps and improving the preparation efficiency of the foamed product 5, the microwave power of the microwave process 4 is preferably greater than or equal to 200W, and more preferably greater than or equal to 400W. For example, the microwave power of the microwave process 4 can be 560W, 800W, 1000W, or 1700W to significantly increase the temperature difference between the rubber matrix and the first carbon material regions.

[0080] It should be noted that microwave irradiation power below 200W may result in the first carbon material not generating enough heat due to microwave heating, that is, the heat generated by microwave heating is insufficient to expand the expandable carbon material and to prevent the formation of a significant temperature gradient within the rubber matrix.

[0081] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: the heating rate of the first carbon material being greater than or equal to 10°C / s.

[0082] Specifically, in this embodiment, by setting the heating rate of the first carbon material to be greater than or equal to 10°C / s, it can ensure that the first carbon material itself and its adjacent area can quickly form local hot spots (for example, the heating rate of the rubber matrix in its adjacent area can be greater than or equal to 10°C / s by using the first carbon material), which facilitates the timely generation of bubbles by the foaming agent, improves foaming efficiency, and shortens the microwave heating time. On the other hand, it can also precisely control the foaming timing and avoid problems such as the foaming agent not being able to foam in time due to excessive heating lag between the foaming agent in the adjacent area of ​​the first carbon material and the first carbon material.

[0083] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: the heating rate of the rubber matrix in the region adjacent to the first carbon material is greater than or equal to 10°C / s.

[0084] Specifically, in this embodiment, the heating rate of the rubber matrix in the region adjacent to the first carbon material is set to be greater than or equal to 10°C / s, so that the foaming agent can generate bubbles in time, improve the foaming efficiency, shorten the microwave heating time, and avoid problems such as the rubber heating up and vulcanization caused by the need for a long microwave heating time due to the heating rate being too low.

[0085] In one embodiment, preparing the compound into a foamed product using a microwave process includes: using a continuous extrusion process while simultaneously using a microwave process to form a foamed product 5 in the form of strips, plates, strips, rods, or hollow tubes.

[0086] Specifically, since the foamed product 5 still has an uncured or incompletely cured surface, by using a continuous extrusion process while simultaneously using a microwave process, it is possible to form strip-shaped, plate-shaped, strip-shaped, rod-shaped, or hollow tubular foamed products 5 more quickly. This makes it easier for the foamed product 5 to be wrapped layer by layer on the surface of the inner rubber layer 7 of the rubber material for hoses during subsequent processing, and further cured and molded through co-curing.

[0087] In addition, the embodiments of this application have better interfacial bonding than the prior art which uses resin or the like as a buoyancy layer. For example, because resin has poor bending performance, it can usually only be molded into tiles and stacked on the surface to be covered. This may cause air bubbles to be generated between the surface to be covered and the surface using resin or the like as a buoyancy layer. The air bubbles are not easy to remove, which seriously affects the interfacial bonding.

[0088] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: preparing the strip-shaped, plate-shaped, or strip-shaped compound 2 into a foamed product 5 using a microwave process.

[0089] Specifically, because foamed product 5 still has an uncured or incompletely cured surface, therefore... Figure 2 and Figure 4 As shown, in this embodiment of the application, a microwave process is used to prepare a foamed product 5 from a strip, plate, or strip-shaped compound 2. This allows the foamed product 5 to be wrapped layer by layer on the surface of the inner rubber layer 7 of the rubber material for hoses during subsequent processing, and then further vulcanized and molded through co-vulcanization.

[0090] In addition, the embodiments of this application have better interfacial bonding than the prior art which uses resin or the like as a buoyancy layer. For example, because resin has poor bending performance, it can usually only be molded into tiles and stacked on the surface to be covered. This may cause air bubbles to be generated between the surface to be covered and the surface using resin or the like as a buoyancy layer. The air bubbles are not easy to remove, which seriously affects the interfacial bonding.

[0091] In some embodiments, when a larger width of foamed product 5 is used for winding and bonding, air bubbles may be generated between the foamed product 5 and the surface to be bonded. Furthermore, the larger width of the foamed product 5 makes it more difficult to remove the air bubbles, which also reduces the adhesion between the foamed product 5 and the surface to be bonded, resulting in delamination between the interfaces and reducing the durability of the final rubber material for the hose.

[0092] Therefore, it is preferable to have a foamed product 5 with a width of 50-200 mm and in the form of a strip or band, which is more conducive to the subsequent layer-by-layer winding process. For example, the strip or band-shaped foamed product 5 can form a tighter fit with the wall to be wound during the winding process, and because it has a smaller width such as 50 mm, 100 mm or 200 mm, the air bubbles formed during the bonding process are also easier to remove, thus ultimately forming a rubber material for hoses with good interfacial bonding.

[0093] In one embodiment, preparing a foamed product 5 from a compound 2 using a microwave process includes: bonding the compound 2 to a conveying device 3, and then preparing the foamed product 5 from the compound 2 using a microwave process; wherein the material of the conveying device 3 includes at least one of microwave-transparent material and metal material, and at least a portion of the compound 2 is not covered by the metal material conveying device 3.

[0094] Specifically, in order to enable the continuous production of foamed product 5, before preparing the mixture 2 into foamed product 5 using microwave technology, the mixture 2 can be first bonded to the conveying device 3, so that the mixture 2 is loaded by the conveying device 3, or the mixture 2 is clamped or fixed by the conveying device 3, thereby improving the preparation efficiency of foamed product 5.

[0095] In order to avoid the simultaneous occurrence of rubber foaming and rubber vulcanization due to excessively high temperature when the compound 2 is prepared into foamed product 5 using microwave technology, it is preferable that the surface of the conveying device 3 in contact with the compound product is lower than the vulcanization temperature of the compound 2 before and after microwave treatment.

[0096] In addition, the embodiment of this application also sets the material of the conveying device 3 to microwave 4 transparent material, so that the conveying device 3 using microwave 4 transparent material can effectively control the surface temperature of the compound 2, and ensure that after the compound 2 is treated by microwave 4, the surface of the conveying device 3 in contact with the compound product is still at a lower temperature than its vulcanization temperature.

[0097] Among them, such as Figure 2 and Figure 4 As shown, the transmission device 3, which is a microwave 4-transmitting material, can be a transmission device 3 formed wholly or partially from one or more of ceramics or quartz; or as... Figure 3 As shown, the conveyor 3, which is a microwave 4-transparent material transmission device, can also be a conveyor belt formed wholly or partially of one or more of ceramics or quartz. Those skilled in the art can choose according to actual needs, and this application does not make specific limitations.

[0098] In addition, the conveying device 3 in this embodiment can also be made of metal. This allows the excellent thermal conductivity of metal to quickly dissipate heat from the surface of the compound 2, precisely controlling the temperature of any surface of at least one pair of specific surfaces 51 of the foamed product 5 to be lower than the vulcanization temperature of the foamed product 5 before and after microwave processing, or precisely controlling any surface of at least one pair of specific surfaces 51 of the foamed product 5 to be unvulcanized or incompletely vulcanized, thereby ensuring the separation of the rubber foaming and rubber vulcanization steps. On the other hand, the high mechanical strength of metal is used to withstand the expansion pressure generated during the foaming of the compound 2, ensuring the regularity of the molding of the foamed product 5.

[0099] Since metal materials are not transparent to microwaves, at least part of the mixture 2 is not covered by the metal material conveying device 3 in order to avoid the inability to process the mixture 2 with microwaves 4.

[0100] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: treating the compound 2 with a constant microwave power 4.

[0101] Specifically, in this embodiment of the application, the power output of the microwave 4 device is kept stable throughout the entire microwave process, and the power output of the microwave 4 device is not adjusted with changes in heating time, temperature of the mixture 2, or foaming state, thereby ensuring the stability of the microwave absorption heating rate of the first carbon material and improving the uniformity of foaming of the foaming agent.

[0102] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: treating the compound 2 with a gradually varying microwave power 4.

[0103] Specifically, in this embodiment, the power output of the microwave 4 device is gradually adjusted according to a preset rule throughout the entire microwave process. This facilitates the adaptation to the heat requirements of different stages of microwave foaming, ensures the compatibility between the microwave absorption heating rate of the first carbon material and the gas production rule of the foaming agent, and improves the uniformity, density, and structural stability of the foamed product 5.

[0104] In one embodiment, preparing a foamed product 5 from a compound 2 using a microwave process includes: treating the compound 2 with at least two intermittently applied microwaves 4; wherein the power of adjacent microwaves 4 is the same or different.

[0105] Specifically, this embodiment of the application adopts a preset mode of "microwave 4 application → pause heating → microwave 4 application" throughout the entire microwave process, and processes the compound 2 in at least two stages, which effectively achieves precise control of the heat accumulation inside the compound 2, avoids local overheating leading to rubber matrix degradation or cell rupture, and ensures that at least one of the specific surfaces 51 of the foamed product 5 is not vulcanized or not fully vulcanized.

[0106] Since the interval between two adjacent microwave heating segments 4 exceeds 60s, the temperature of the hot spot area in the mixture 2 will drop significantly, and the temperature difference between different areas in the entire mixture 2 will be significantly reduced. Therefore, when the mixture 2 is processed with microwave power applied at least twice, the interval between two adjacent microwave heating segments 4 is preferably no more than 60s.

[0107] In addition, when the compound 2 is treated with microwaves 4 applied in multiple intermittent segments, the microwaves 4 applied in multiple intermittent segments can also be gradually applied microwaves 4 to meet the different production requirements of the foamed product 5.

[0108] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: the microwave heating time is 10~1000s.

[0109] Specifically, the heating time for the microwave process should be just enough to cause the foaming agent to foam. For example, it can be determined whether the foaming agent has foamed by observing the cross-sectional morphology of the foamed product 5.

[0110] Although the time required varies depending on the type of foaming agent, the amount of first carbon material added, or the heating power of microwave 4, when using unexpanded expandable graphite and / or AC foaming agent as the foaming agent, excessive heating time may cause the mixture 2 to heat up to excessively high temperatures, resulting in excessive sulfidation or even carbonization. Insufficient heating time is not enough for the foaming agent to foam. Therefore, the heating time of the microwave process should be in the range of 10 to 600 seconds, more preferably in the range of 30 to 420 seconds.

[0111] In one embodiment, preparing the compound 2 into a foamed product 5 using a microwave process includes: placing at least one pair of specific surfaces of the compound 2 in a mold or fixing it with a fixing member and then performing microwave processing, wherein the temperature of the surface of the mold or fixing member in contact with at least one pair of specific surfaces of the compound 2 is lower than the vulcanization temperature of the compound 2 before and after preparing the compound 2 into a foamed product 5 using a microwave process.

[0112] Specifically, in this embodiment of the application, by placing at least a pair of specific surfaces of the mixture 2 in a mold or fixing it with a fixing member, and then performing microwave processing to form a foamed product 5, the resulting foamed product 5 can have a certain shape. Thus, in such a process, in order to ensure that the resulting foamed product 5 has at least a pair of specific unvulcanized or incompletely vulcanized surfaces, the temperature of the surface of the mold or fixing member in contact with at least a pair of specific surfaces of the mixture 2 needs to be lower than the vulcanization temperature of the mixture before and after the mixture 2 is prepared into a foamed product 5 using microwave processing.

[0113] In this way, a foamed product 5 with a certain shape and a pair of specific surfaces 51 that are not vulcanized or not fully vulcanized can be obtained.

[0114] S103, at least one pair of specific surfaces 51 or two portions of a ring of surfaces of the foamed product 5 are bonded, compounded or laminated with two layers of uncured or incompletely cured rubber 6 to form a composite rubber. It should be noted that, since the foamed product 5 is usually required to undergo further compounding and vulcanization molding when it is used in marine engineering pipes, in order to form the final hose, it is preferable to bond, compound, or laminate at least one pair of specific surfaces 51 or two parts of a ring of surfaces of the foamed product 5 with two layers of unvulcanized or incompletely vulcanized rubber 6 to form a composite rubber. That is, by preparing the foamed product 5 into a composite rubber, the bending performance of the rubber material for the final hose can be further improved.

[0115] In the field of marine engineering, the foamed product 5 formed by microwave heating 4 needs to have at least one pair of specific surfaces 51, and these at least one pair of specific surfaces 51 are two opposing surfaces so that the two surfaces can be bonded to different rubber layers and vulcanized together to form a hose for marine engineering. Therefore, in order to achieve the vulcanization of the hose, the at least one pair of specific surfaces 51 needs to have the following characteristics: the temperature of any surface of the at least one pair of specific surfaces 51 is lower than the vulcanization temperature of the foamed product 5 before and after microwave treatment; or, any surface of the at least one pair of specific surfaces 51 is not vulcanized or not fully vulcanized.

[0116] Furthermore, in other embodiments, since in the field of marine engineering, the foamed product 5 formed by microwave heating 4 needs to have two parts in a ring surface, and the two parts in the ring surface are two opposing parts, so that the two parts can be bonded to different rubber layers and vulcanized together to form a rubber hose for marine engineering, in order to achieve the vulcanization of the rubber hose, the two parts in the ring surface need to have the following characteristics: the temperature of either part in the ring surface is lower than the vulcanization temperature of the foamed product 5 before and after microwave treatment; or, either part in the ring surface is not vulcanized or not fully vulcanized.

[0117] In one embodiment, bonding, compounding, or stacking at least one pair of specific surfaces 51 or two portions of a ring of surfaces of foamed product 5 with two layers of unvulcanized or incompletely vulcanized rubber 6 to form a composite rubber comprises: wrapping one of the at least one pair of specific surfaces 51 around the surface of an unvulcanized or incompletely vulcanized rubber 6, and then bonding, wrapping, or stacking another unvulcanized or incompletely vulcanized rubber 6 on the other surface of the at least one pair of specific surfaces 51 to form a laminated composite rubber.

[0118] Specifically, such as Figure 5As shown, in this embodiment of the application, one of at least a pair of specific surfaces 51 is first wrapped and bonded to the surface of an unvulcanized or incompletely vulcanized rubber 6 (that is, one of at least a pair of specific surfaces 51 is wrapped and bonded to the inner rubber 7), and then another unvulcanized or incompletely vulcanized rubber 6 is bonded, wrapped or stacked to the other surface of the at least a pair of specific surfaces 51, so as to facilitate the formation of a laminated composite rubber.

[0119] In one embodiment, bonding, compounding, or stacking at least one pair of specific surfaces 51 or two portions of a ring surface of foamed product 5 with two layers of unvulcanized or incompletely vulcanized rubber 6 to form a composite rubber comprises: wrapping one portion of the two portions of a ring surface around and bonding it to the surface of an unvulcanized or incompletely vulcanized rubber 6, and then bonding, wrapping, or stacking another unvulcanized or incompletely vulcanized rubber 6 onto the other portion of the two portions of a ring surface to form a laminated composite rubber.

[0120] Specifically, in this embodiment, one of the two parts of a ring surface is first wrapped and adhered to the surface of an unvulcanized or incompletely vulcanized rubber 6, and then another unvulcanized or incompletely vulcanized rubber 6 is adhered, wrapped, or stacked on the other part of the two parts of the ring surface, so as to facilitate the formation of a laminated composite rubber, thereby enhancing the bending performance and service life of the rubber material for hoses.

[0121] S104 is a rubber material for hoses, which is formed by vulcanizing composite rubber using a vulcanization process.

[0122] It should be noted that, since the foamed product 5 contains a first carbon material that can be heated by microwave 4 and the unvulcanized or incompletely vulcanized rubber 6 after at least one pair of specific surfaces 51 or two parts of a ring of surfaces are bonded, compounded or laminated with two layers of unvulcanized or incompletely vulcanized rubber 6, the resulting composite rubber can also be vulcanized as a whole by a vulcanization process, without the need to vulcanize the multi-layer rubber in segments. That is, by using the foamed product 5 in the composite rubber as a heat source to heat itself and the adjacent unvulcanized or incompletely vulcanized rubber 6, the unvulcanized or incompletely vulcanized rubber 6 is heated by the first carbon material. This not only effectively simplifies the vulcanization process steps and eliminates the significant phase interface between the foamed product 5 (buoyancy layer) and the rubber layer, making the bond between the buoyancy layer and the rubber layer tighter and less prone to peeling, thus avoiding the problem of buoyancy layer failure due to water ingress into the hose, but also improves the heating uniformity of the rubber during vulcanization and improves the preparation quality of the rubber material for hoses.

[0123] In one embodiment, the process of vulcanizing composite rubber to form rubber material for hoses includes: during the vulcanization process of composite rubber, microwave technology is used to assist in heating the composite rubber to form rubber material for hoses; wherein at least one of the two unvulcanized or incompletely vulcanized rubber layers 6 includes a second carbon material, the second carbon material being a carbon material containing a graphene structure.

[0124] Specifically, in this embodiment, microwave-assisted heating of the composite rubber is achieved. On the one hand, the first carbon material in the foamed product 5 can absorb microwaves 4 and form local hot spots to heat the first carbon material itself and its adjacent area. On the other hand, the second carbon material in the uncured or incompletely cured rubber 6 can form hot spots within its matrix under the assistance of microwave 4 irradiation, just like the first carbon material, thus achieving heating from within the rubber. This effectively improves the curing efficiency of the composite rubber.

[0125] In order to ensure that the composite rubber in the subsequent vulcanization process can be heated more synchronously and uniformly, it is preferable that at least one of the two unvulcanized or incompletely vulcanized rubber layers 6 includes a second carbon material.

[0126] Therefore, since the second carbon material can generate heat by absorbing microwaves 4, the uncured or incompletely cured rubber 6 containing the second carbon material can form hot spots within its matrix under the assistance of microwave 4 irradiation, similar to the foamed product 5. This enables heating from within the rubber.

[0127] In addition, the second carbon material may include at least one of graphene, graphene oxide, graphite, and expandable carbon materials.

[0128] For example, graphene can be single-layer graphene, multi-layer graphene, or stacked graphene; graphene oxide can be single-layer graphene oxide, multi-layer graphene oxide, or stacked graphene oxide; expandable carbon materials can include unexpanded expandable graphite, foaming agent intercalated graphite, graphene, or graphene oxide.

[0129] It should be noted that since a significant temperature gradient is no longer required during the vulcanization process, microwave technology can be used to vulcanize the composite rubber into rubber material for hoses during the subsequent vulcanization process. That is, microwave technology is used to heat or assist in heating the composite rubber to vulcanize it into rubber material for hoses.

[0130] It should be noted that, unlike when using microwave technology to heat or assist in heating composite rubber, the process does not require a high irradiation power or a specific irradiation power to material power-mass ratio, which is not necessary when using microwave technology to prepare the compound 2 into foamed product 5.

[0131] According to another embodiment of this application, a rubber hose is provided, which is prepared using a rubber material for rubber hoses prepared by the method for preparing rubber material for rubber hoses as described in the embodiments of this application.

[0132] In some embodiments, the hose is a marine engineering hose.

[0133] The present application will be further described below with reference to specific embodiments.

[0134] Example 1 S111, mix 5 parts expandable graphite, 100 parts butadiene rubber, 1 part sulfur and 1.5 parts vulcanization accelerator TT to obtain compound A.

[0135] S112, obtain 10g of compound A, clamp the opposite sides of compound A with ceramic sheets, and heat with a microwave of 560W for 210s to form foamed product A. The temperature of the opposite sides of compound A is lower than the vulcanization temperature of compound A before and after microwave heating treatment.

[0136] S113, the two opposite sides of the foamed product A are bonded to the uncured rubber A to form a composite rubber A. The uncured rubber A consists of 100 parts natural rubber, 40 parts carbon black, 4 parts sulfur, and 4 parts accelerator CZ.

[0137] S114, composite rubber A is vulcanized for 150 seconds using a 560W microwave heater, and then naturally cooled to room temperature to form rubber material A for hoses. The cross-section of rubber material A for hoses is shown below. Figure 6 As shown, foamed product A and uncured rubber A are bonded together and cannot be separated.

[0138] Example 2 S211, mix 6 parts AC foaming agent, 5 parts expandable graphite, 100 parts cis-butadiene rubber, 1 part sulfur and 1.5 parts vulcanization accelerator TT to obtain compound B.

[0139] S212, 8g of compound B was obtained and heated with a 400W microwave for 180s to form foamed product B. The temperatures of both sides of compound B were lower than its vulcanization temperature before and after microwave heating.

[0140] S213, the two opposite sides of the foamed product B are bonded to the uncured rubber B to form a composite rubber B. The uncured rubber B consists of 100 parts natural rubber, 40 parts carbon black, 4 parts sulfur, and 4 parts accelerator CZ.

[0141] S214 is vulcanized with 560W microwave heating for 150s to form composite rubber B, which is then naturally cooled to room temperature, thus forming rubber material B for hoses. The cross-section of rubber material B for hoses is shown below. Figure 7As shown, the foamed product B and the uncured rubber B are bonded together and cannot be separated.

[0142] Example 3 S311, 12 parts AC foaming agent, 4 parts expandable graphite, 200 parts butadiene rubber, 2 parts sulfur and 3 parts vulcanization accelerator TT are mixed to obtain compound C. Compound C is continuously extruded in strip form at a speed of 150 g / min, and the extruded compound C is cut into 20g plates.

[0143] S312, 20g of plate-shaped compound C is obtained. The two opposite sides of the plate-shaped compound C are clamped with ceramic sheets and heated with microwaves at 800W power for 100s to form foamed product C. The temperature of the two opposite sides of the compound C is lower than the vulcanization temperature of the compound C before and after microwave heating treatment.

[0144] S313 involves bonding the two opposite sides of the foamed product C to unvulcanized rubber C to form a composite rubber C. The unvulcanized rubber C consists of 100 parts natural rubber, 10 parts graphene, 4 parts sulfur, and 4 parts accelerator CZ.

[0145] S314 is formed by hot-pressing and vulcanizing composite rubber C at 160℃ for 5 minutes, followed by natural cooling to room temperature, to create rubber material C for hoses. In this rubber material C, the foamed product C and the unvulcanized rubber C are bonded together and cannot be peeled off.

[0146] Example 4 S411, mix 15 parts expandable graphite, 100 parts butadiene rubber, 1 part sulfur and 1.5 parts vulcanization accelerator TT to obtain compound D.

[0147] S412, obtain 10g of compound D, roll 10g of compound D into a hollow tube shape, clamp two parts of the surface of the hollow tube compound D with a ceramic sheet, and heat with a microwave of 1000W power for 90s to form foamed product D. The temperature of the two parts of the surface of compound D is lower than the vulcanization temperature of compound D before and after microwave heating treatment.

[0148] S413, two portions of the surface of the foamed product D are bonded to the uncured rubber D to form a composite rubber D. The uncured rubber D consists of 100 parts natural rubber, 10 parts silica, 4 parts sulfur, and 4 parts accelerator CZ.

[0149] S414 is composite rubber D, which is hot-pressed and vulcanized at 160℃ for 5 minutes and then naturally cooled to room temperature to form rubber material D for hoses. In this rubber material D, the foamed product D and the unvulcanized rubber D are bonded together and cannot be peeled off.

[0150] Example 5 S511, 40 parts of AC foaming agent, 20 parts of expandable graphite, 200 parts of cis-butadiene rubber, 2 parts of sulfur and 3 parts of vulcanization accelerator TT are mixed to obtain compound E. Compound E is continuously extruded into a hollow tubular shape at a speed of 150 g / min.

[0151] S512, 25g of hollow tubular compound E was obtained. Two parts of the surface of the hollow tubular compound E were clamped with ceramic sheets and heated with microwaves at 1800W for 30s to form foamed product E. The temperature of the two parts of the surface of compound E was lower than the vulcanization temperature of compound E before and after microwave heating treatment.

[0152] S513, two portions of the surface of the foamed product E are bonded to uncured rubber E to form composite rubber E. The uncured rubber E consists of 100 parts natural rubber, 40 parts carbon black, 4 parts sulfur, and 4 parts accelerator CZ.

[0153] S514, composite rubber E is vulcanized for 150 seconds using microwave heating with a power of 1000W, and then naturally cooled to room temperature to form rubber material E for hoses. In this rubber material E, the foamed product E and the unvulcanized rubber E are bonded together and cannot be separated.

[0154] Example 6 S611, 120 parts of AC foaming agent, 12 parts of graphene, 400 parts of cis-butadiene rubber, 2 parts of sulfur and 3 parts of vulcanization accelerator TT are mixed to obtain compound F. Compound F is continuously extruded into a hollow tubular shape at a speed of 100 g / min and 1.5 m / min.

[0155] S612, during extrusion, for every 0.4m of extruded hollow tubular compound F, two portions of the surface of the hollow tubular compound F are clamped with ceramic sheets and heated with microwaves at 1800W for 20s to form foamed product F. The temperature of the two portions of the surface of compound F is lower than the vulcanization temperature of compound F both before and after microwave heating treatment.

[0156] S613 involves bonding two portions of the surface of a foamed product F to uncured rubber F to form a composite rubber F. The uncured rubber F consists of 100 parts natural rubber, 40 parts carbon black, 4 parts sulfur, and 4 parts accelerator CZ.

[0157] S614 is a composite rubber F that is vulcanized for 150 seconds using microwave heating with a power of 1000W, and then naturally cooled to room temperature to form a rubber material F for hoses. In this rubber material F, the foamed product F and the unvulcanized rubber F are bonded together and cannot be separated.

[0158] Example 7 S711, 15 parts AC foaming agent, 15 parts expandable graphite, 100 parts cis-butadiene rubber, 1 part sulfur and 1.5 parts vulcanization accelerator TT are mixed to obtain compound G. Compound G is continuously extruded in strip form at a speed of 200 g / min, and the extruded compound G is cut into 30g strips.

[0159] S712, obtain 30g of strip-shaped compound G, clamp two parts of the surface of the strip-shaped compound G with a ceramic sheet, and heat with a microwave of 1800W for 15s to form a foamed product G. The temperature of the two parts of the surface of the compound G is lower than the vulcanization temperature of the compound G both before and after microwave heating.

[0160] S713, firstly, a foamed product G is wound around a layer of unvulcanized rubber G, and then another layer of unvulcanized rubber G is wound around the outer surface of the foamed product G to form a composite rubber G. The unvulcanized rubber G consists of 100 parts natural rubber, 40 parts carbon black, 4 parts sulfur, and 4 parts accelerator CZ.

[0161] S714, composite rubber G is vulcanized for 4 minutes using microwave heating with a power of 1800W, and then naturally cooled to room temperature to form rubber material G for hoses. In this rubber material G, the foamed product G and the unvulcanized rubber G are bonded together and cannot be peeled off.

[0162] The rubber materials for hoses prepared in Examples 1 to 7 were transported to a testing device for testing. The tests showed that the rubber materials for hoses prepared in Examples 1 to 7 exhibited good bending performance and better interfacial bonding between the buoyancy layer and other rubber layers.

[0163] The above embodiments mainly describe the differences between the various embodiments. As long as the different optimization features between the various embodiments are not contradictory, they can be combined to form a better embodiment. For the sake of brevity, they will not be elaborated here.

[0164] While specific embodiments of this application have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and are not intended to limit the scope of this application. Those skilled in the art should understand that modifications can be made to the above embodiments without departing from the scope and spirit of this application. The scope of this application is defined by the appended claims.

Claims

1. A method for preparing rubber material for hoses, characterized in that, include: The foaming agent, rubber matrix, additives and first carbon material are mixed to form a compound; The mixture was prepared into a foamed product using a microwave process. The foamed product is bonded, laminated, or stacked with two layers of unvulcanized or incompletely vulcanized rubber to form a composite rubber. The composite rubber is vulcanized using a vulcanization process to form a rubber material for hoses. Wherein, the first carbon material is a carbon material containing a graphene structure; the pair of specific surfaces are two opposing surfaces; the two parts of the ring surface are two opposing parts; and the temperature of either the pair of specific surfaces or the two parts of the ring surface is lower than the vulcanization temperature of the foamed product before and after microwave processing, or either the pair of specific surfaces or the two parts of the ring surface is not vulcanized or not fully vulcanized.

2. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the first carbon material includes at least one of graphene, graphene oxide, graphite, and expandable carbon material; Wherein, the graphene is single-layer graphene, multi-layer graphene, or stacked graphene; the graphene oxide is single-layer graphene oxide, multi-layer graphene oxide, or stacked graphene oxide; the expandable carbon material includes unexpanded expandable graphite, foaming agent intercalated graphite, graphene, or graphene oxide. Furthermore, when the first carbon material includes the expandable carbon material, the expandable carbon material is also considered as a type of foaming agent.

3. The method for preparing rubber material for hoses according to claim 1, characterized in that, When the foaming agent is not a carbon material, the vaporization or decomposition temperature of the foaming agent is less than or equal to 300°C; And / or, when the first carbon material contains expandable carbon material, the foaming agent vaporizes or decomposes to produce gas at a temperature not exceeding a first temperature; wherein, the first temperature is the temperature at which the expandable carbon material loses 30% of its mass under an inert gas atmosphere.

4. The method for preparing rubber material for hoses according to claim 1, characterized in that, The mass ratio of the foaming agent to the rubber matrix is ​​3~80:100; Furthermore, the mass ratio of the first carbon material to the rubber matrix is ​​1~80:

100.

5. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the mixture of foaming agent, rubber matrix, additives and first carbon material to form a compound includes: A continuous extrusion process is used to mix foaming agent, rubber matrix, additives and first carbon material to form a compound, and the compound is continuously discharged in the form of strips, plates, strips, rods or hollow tubes. Alternatively, the foaming agent, rubber matrix, additives and first carbon material are mixed to form a compound, and the compound is cut and / or spliced ​​to form a strip, plate, strip, rod or hollow tubular compound.

6. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the preparation of the foamed product from the compound using a microwave process includes: The ratio of the power of microwave radiation received by the compound to the mass of the rubber matrix and the first carbon material is greater than or equal to 40 W / g. And / or, the heating rate of the first carbon material is greater than or equal to 10 °C / s; And / or, the heating rate of the rubber matrix in the region adjacent to the first carbon material is greater than or equal to 10°C / s.

7. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the preparation of the foamed product from the compound using a microwave process includes: The continuous extrusion process is combined with microwave processing to form foamed products in the form of strips, plates, strips, rods or hollow tubes. Alternatively, microwave processes can be used to prepare foamed products from strip-shaped, plate-shaped, strip-shaped, rod-shaped, or hollow tubular mixtures.

8. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the preparation of the foamed product from the compound using a microwave process includes: The mixture is treated with constant microwave power, or with gradually varying microwave power, or with at least two intermittently applied microwaves. Among them, the power of two adjacent microwave segments may be the same or different.

9. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, bonding, laminating, or stacking at least one pair of specific surfaces or two portions of a ring of the foamed product with two layers of uncured or incompletely cured rubber to form a composite rubber includes: After wrapping and bonding one of the two parts of the pair of specific surfaces or a ring of surfaces to the surface of an unvulcanized or incompletely vulcanized rubber, another unvulcanized or incompletely vulcanized rubber is then bonded, wrapped, or stacked on the other surface or part of the pair of specific surfaces or a ring of surfaces to form a laminated composite rubber.

10. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the composite rubber is vulcanized using a vulcanization process to form a rubber material for hoses, comprising: During the vulcanization process of the composite rubber, microwave technology is used to assist in heating the composite rubber to form a rubber material for hoses. In this embodiment, at least one of the two layers of uncured or incompletely cured rubber includes a second carbon material, which is a carbon material containing a graphene structure.

11. The method for preparing rubber material for hoses according to claim 1, characterized in that, Preferably, the preparation of the foamed product from the compound using a microwave process includes: The mixture is microwave-processed after at least one pair of specific surfaces are placed in a mold or fixed by a fixture, and the temperature of the surface of the mold or fixture in contact with at least one pair of specific surfaces of the mixture is lower than the vulcanization temperature of the mixture before and after the mixture is prepared into a foamed product by microwave process.

12. A rubber hose, characterized in that, The hose is prepared using a rubber material for hoses prepared by any one of the methods described in claims 1 to 11.

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