Low-toxicity flame-retardant composite material and preparation method thereof

Abstract

The invention provides a low-toxicity flame-retardant composite material and a preparation method thereof. The low-toxicity flame-retardant composite material comprises fibers and a resin system, wherein the resin system comprises modified vinyl resin, a curing agent and an accelerant. The low-toxicity flame-retardant composite material can meet the use requirements of ship cabins on fire prevention, flame retardance and low smoke toxicity, has excellent marine environment resistance, light weight and high strength, and is beneficial to realizing the aims of light weight, low carbon and environmental protection of ships; meanwhile, the composite material has excellent corrosion resistance and weather resistance, the service life of corresponding application products can be prolonged, the maintenance cost is reduced, and the composite material is suitable for the harsh marine environment.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to a low-toxic flame-retardant composite material and a preparation method thereof. Background Art

[0002] In the context of the new era, with the increasing global awareness of environmental protection and the improvement of energy efficiency requirements, the shipbuilding industry is gradually developing in the direction of high quality, high efficiency, and green environmental protection. As one of the key technologies to improve the comprehensive performance of ships, ship weight reduction design has a significant effect on increasing navigation speed, increasing load capacity, enhancing ship flexibility, and reducing fuel consumption and pollutant emissions. It is an important way to achieve green shipping.

[0003] Traditional hull structural materials mainly include steel and aluminum alloy. Steel is widely used due to its high strength and good processing performance, but it has the disadvantages of being heavy and prone to corrosion, which poses a challenge to the energy efficiency and life of ships. Although aluminum alloy materials reduce weight to a certain extent, their welding process is complicated and their fatigue resistance is relatively poor, which limits their widespread application in shipbuilding.

[0004] In order to overcome the limitations of traditional metal materials, fiber-reinforced composite materials have received extensive attention and application in rail transportation, wind power generation, aerospace, and shipbuilding due to their excellent properties such as light weight, high strength, and corrosion resistance. Especially in the field of ships, composite materials have been widely used in external structures such as hulls, superstructures, and external outfitting, effectively achieving the goals of weight reduction and corrosion resistance, and significantly improving the overall performance of ships.

[0005] Although the application of composite materials in the external structure of ships has achieved remarkable results, their application in ship cabins is relatively lagging. This is mainly due to the high fire protection level requirements for ship cabins, and composite materials may produce toxic gases during combustion, posing a serious threat to the safety of personnel and property. Specifically, fiber-reinforced composite materials are composed of fibers and resins. The decomposition temperature of the fibers is relatively high, but the values ​​can decompose and burn at relatively low temperatures, and produce toxic gases including carbon monoxide, cyanide, sulfide, nitrogen oxides, etc. These gases quickly diffuse in the confined space of the cabin, which will greatly increase the hazard of fire.

[0006] Given the complex internal structure of the cabin, the closed space, and the narrow passages and entrances, it is difficult to evacuate personnel once a fire occurs. In addition, there are many combustible materials in the cabin and the fire spreads rapidly. Therefore, the development of low-toxic flame-retardant composite materials is urgently needed and of great significance for promoting cabin lightweighting, energy saving and environmental protection. Summary of the invention

[0007] In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a low-toxic flame-retardant composite material and a preparation method thereof. The low-toxic flame-retardant composite material can meet the requirements of fire retardancy and low smoke toxicity in ship cabins, has excellent resistance to marine environments and light weight and high strength, and is conducive to achieving the goals of lightweight, low-carbon and environmentally friendly ships.

[0008] To achieve the above-mentioned and other related purposes, the present invention provides a low-toxic flame-retardant composite material, including fibers and a resin system;

[0009] The resin system comprises a modified vinyl resin, a curing agent and an accelerator.

[0010] Optionally, the resin system comprises, by weight: 90 to 95 parts of modified vinyl resin, 4 to 8.5 parts of curing agent, and 1 to 1.5 parts of accelerator.

[0011] Optionally, the modified vinyl resin consists of a vinyl resin and a modifier, and the modifier is selected from one or both of cage-type polysiloxane and ammonium polyphosphate.

[0012] Optionally, the weight of the modifier is 15% to 20% of the weight of the vinyl resin.

[0013] Optionally, the curing agent is selected from one or more of methyl ethyl ketone peroxide, acetylacetone peroxide and diketone acrylamide adduct.

[0014] Optionally, the promoter is selected from one or both of cobalt octoate and cobalt naphthenate.

[0015] Optionally, the viscosity of the resin system is between 150 mPa·s and 500 mPa·s.

[0016] The viscosity of the resin system used in this embodiment is convenient for introducing the resin system through the rubber tube in the preparation method, and also has good interface performance with the fiber. If the viscosity of the resin system is too high, it will be difficult to pour into the rubber tube; if the viscosity of the resin system is too low, the interface performance with the fiber will be relatively low and it will not be easy to bond with the fiber.

[0017] Optionally, the fiber includes a fiber fabric, the fiber fabric is woven using one of carbon fiber, glass fiber, basalt fiber, or aramid fiber, and the fiber fabric is in the form of plain cloth or twill cloth.

[0018] The fiber used in this embodiment is a fiber fabric. The strength of the fiber fabric is higher than that of the fiber, which is beneficial to improving the mechanical properties of the composite material.

[0019] The present application also provides a method for preparing a low-toxic flame-retardant composite material, comprising the following steps:

[0020] At room temperature, the vinyl resin reacts with the modifier to obtain a modified vinyl resin;

[0021] At room temperature, the vinyl resin, curing agent and accelerator react to obtain a resin system;

[0022] The resin system and the fiber are formed by a vacuum-assisted resin transfer molding process to obtain a low-toxic flame-retardant composite material.

[0023] Optionally, the resin system and the fiber are formed by a vacuum assisted resin transfer molding process, which specifically includes the following steps:

[0024] Placing the gel coat, the fiber, the release cloth, the guide net and the vacuum bag in the mold in sequence;

[0025] Vacuuming, after reaching a preset vacuum degree, introducing the resin system through a rubber guide tube;

[0026] After the resin system is introduced, the composite material is cured.

[0027] Preferably, the curing temperature of the composite material is between 80° C. and 120° C., and the curing time is between 10 h and 24 h.

[0028] The present application also provides an application of a low-toxic flame-retardant composite material in a ship cabin.

[0029] As described above, the low-toxic flame-retardant composite material and the preparation method thereof of the present application have the following beneficial effects:

[0030] The low-toxic flame-retardant composite material provided by the present application modifies the vinyl resin by a modifier, which significantly improves the flame-retardant properties of the vinyl resin, so that it can meet the fire-retardant requirements of ship cabins; the toxic gas produced by the modified vinyl resin when decomposed at high temperature is significantly reduced, reducing the toxicity and harm of the smoke. The low-toxic flame-retardant composite material can meet the requirements of fire-retardant and low smoke toxicity of ship cabins, and has excellent resistance to marine environment and light weight and high strength, which is conducive to achieving the goal of lightweight, low-carbon and environmentally friendly ships; at the same time, the composite material has excellent corrosion resistance and weather resistance, which can extend the service life of the corresponding application products, reduce maintenance costs, and is suitable for harsh marine environments. DETAILED DESCRIPTION

[0031] The present application is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and are not used to limit the scope of protection of the present application.

[0032] The following describes the implementation of the present application through specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification. The present application can also be implemented or applied through other different specific implementations, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application.

[0033] Example 1

[0034] This embodiment provides a low-toxic flame-retardant composite material, which is composed of 60% fiber and 40% resin system by weight percentage;

[0035] The resin system comprises 92 parts of modified vinyl resin, 6.5 parts of methyl ethyl ketone peroxide and 1.5 parts of cobalt octoate in parts by weight; the modified vinyl resin consists of 84% of vinyl resin and 16% of cage-type polysiloxane in parts by weight.

[0036] This embodiment also provides a method for preparing a low-toxic flame-retardant composite material, comprising the following steps:

[0037] At room temperature, the vinyl resin and the cage-type polysiloxane are uniformly mixed according to the above weight percentages, and after reaction, a modified vinyl resin is obtained;

[0038] At room temperature, the modified vinyl resin, methyl ethyl ketone peroxide and cobalt octanoate are uniformly mixed according to the above weight proportions, and after reaction, a resin system is obtained, and the viscosity of the resin system is 300 mPa·s;

[0039] Low-toxic flame-retardant composite materials are prepared by vacuum-assisted resin transfer molding process, which includes laying gel coat, carbon fiber plain cloth, release cloth, guide net and vacuum bag in the mold in sequence; vacuuming, and after reaching the required vacuum degree, introducing the resin system through the rubber guide hose; after the resin system is introduced, the composite material is cured at 100°C for 18 hours.

[0040] Example 2

[0041] This embodiment provides a low-toxic flame-retardant composite material, which is composed of 60% fiber and 40% resin system by weight percentage;

[0042] The resin system comprises 94 parts of modified vinyl resin, 5 parts of acetylacetone peroxide and 1 part of cobalt octanoate in parts by weight; the modified vinyl resin consists of 82% of vinyl resin and 18% of polyphosphoric acid amine in parts by weight.

[0043] This embodiment also provides a method for preparing a low-toxic flame-retardant composite material, comprising the following steps:

[0044] At room temperature, the vinyl resin and the polyphosphate amine are mixed uniformly according to the above weight percentages, and after reaction, a modified vinyl resin is obtained;

[0045] At room temperature, the modified vinyl resin, acetylacetone peroxide and cobalt octanoate are uniformly mixed according to the above weight proportions, and after reaction, a resin system is obtained, and the viscosity of the resin system is 260 mPa·s;

[0046] Low-toxic flame-retardant composite materials are prepared by vacuum-assisted resin transfer molding process, which includes laying gel coat, carbon fiber twill cloth, release cloth, guide net and vacuum bag in the mold in sequence; vacuuming, and after reaching the required vacuum degree, introducing the resin system through the rubber guide hose; after the resin system is introduced, the composite material is cured at 120°C for 15 hours.

[0047] Example 3

[0048] This embodiment provides a low-toxic flame-retardant composite material, which is composed of 60% fiber and 40% resin system by weight percentage;

[0049] The resin system comprises 90 parts of modified vinyl resin, 8.5 parts of methyl ethyl ketone peroxide and 1.5 parts of cobalt cyclohexane acid in parts by weight; the modified vinyl resin consists of 80% of vinyl resin and 20% of polyphosphoric acid amine in parts by weight.

[0050] This embodiment also provides a method for preparing a low-toxic flame-retardant composite material, comprising the following steps:

[0051] At room temperature, the vinyl resin and the polyphosphate amine are mixed uniformly according to the above weight percentages, and after reaction, a modified vinyl resin is obtained;

[0052] At room temperature, the modified vinyl resin, methyl ethyl ketone peroxide and cobalt cyclopentaneate are uniformly mixed according to the above weight proportions, and after reaction, a resin system is obtained, and the viscosity of the resin system is 190 mPa·s;

[0053] Low-toxic flame-retardant composite materials are prepared by vacuum-assisted resin transfer molding process, which includes laying gel coat, glass fiber plain cloth, release cloth, guide net and vacuum bag in the mold in sequence; vacuuming, and after reaching the required vacuum degree, introducing the resin system through the rubber guide hose; after the resin system is introduced, the composite material is cured at 120°C for 15 hours.

[0054] Example 4

[0055] This embodiment provides a low-toxic flame-retardant composite material, which is composed of 60% fiber and 40% resin system by weight percentage;

[0056] The resin system comprises 93.5 parts of modified vinyl resin, 6 parts of diketone acrylamide adduct and 1.5 parts of cobalt cyclohexane in parts by weight; the modified vinyl resin consists of 85% of vinyl resin and 15% of cage-type polysiloxane in parts by weight.

[0057] This embodiment also provides a method for preparing a low-toxic flame-retardant composite material, comprising the following steps:

[0058] At room temperature, the vinyl resin and the cage-type polysiloxane are uniformly mixed according to the above weight percentages, and after reaction, a modified vinyl resin is obtained;

[0059] At room temperature, the modified vinyl resin, diketone acrylamide adduct and cobalt cyclopentaneate are uniformly mixed according to the above weight proportions, and after reaction, a resin system is obtained, and the viscosity of the resin system is 400 mPa·s;

[0060] Low-toxic flame-retardant composite materials are prepared by vacuum-assisted resin transfer molding process, which includes laying gel coat, basalt fiber plain cloth, release cloth, guide net and vacuum bag in the mold in sequence; vacuuming, and after reaching the required vacuum degree, introducing the resin system through the rubber guide hose; after the resin system is introduced, the composite material is cured at 90°C for 20 hours.

[0061] Example 5

[0062] This embodiment provides a low-toxic flame-retardant composite material, which is composed of 60% fiber and 40% resin system by weight percentage;

[0063] The resin system comprises 95 parts of modified vinyl resin, 4 parts of diketone acrylamide adduct and 1 part of cobalt octanoate in parts by weight; the modified vinyl resin consists of 81% of vinyl resin and 19% of cage-type polysiloxane in parts by weight.

[0064] This embodiment also provides a method for preparing a low-toxic flame-retardant composite material, comprising the following steps:

[0065] At room temperature, the vinyl resin and the cage-type polysiloxane are uniformly mixed according to the above weight percentages, and after reaction, a modified vinyl resin is obtained;

[0066] At room temperature, the modified vinyl resin, diketone acrylamide adduct and cobalt octanoate are uniformly mixed according to the above weight proportions, and after reaction, a resin system is obtained, and the viscosity of the resin system is 450 mPa·s;

[0067] Low-toxic flame-retardant composite materials are prepared by vacuum-assisted resin transfer molding process, which includes laying gel coat, carbon fiber twill cloth, release cloth, guide net and vacuum bag in the mold in sequence; vacuuming, and after reaching the required vacuum degree, introducing the resin system through the rubber guide hose; after the resin system is introduced, the composite material is cured at 110°C for 12 hours.

[0068] Comparative Example 1

[0069] The difference between the low-toxic flame-retardant composite material provided in Comparative Example 1 and Example 1 is that:

[0070] No cage-type polysiloxane is added, that is, the vinyl resin used is an unmodified vinyl resin.

[0071] Comparative Example 2

[0072] The difference between the low-toxic flame-retardant composite material provided in Comparative Example 2 and Example 1 is that:

[0073] The resin system includes 89 parts of modified vinyl resin, 8.5 parts of methyl ethyl ketone peroxide and 2.5 parts of cobalt octoate in parts by weight.

[0074] The low-toxic flame-retardant composite materials of Examples 1 to 5, Comparative Examples 1 and 2 were tested for mechanical properties, flame retardancy and smoke toxicity. The tensile strength test was carried out according to GB / T 1447-2005, the bending strength test was carried out according to GB / T 1449-2005, the combustion behavior of the material was measured by the oxygen index method according to GB / T 2406.2-2009, and the smoke toxicity test was carried out according to the smoke and toxicity test in Part 2 of Appendix 1 of the 2010 International Fire Test Procedure Application Rules. The performance test data are shown in Table 1.

[0075] Table 1

[0076] sample Tensile strength MPa Full strength MPa Smoke density Oxygen index% Example 1 435.3 520.9 172.3 34.6 Example 2 411.6 536.7 163.9 36.7 Example 3 398.9 489.3 189.5 31.9 Example 4 437.0 530.1 178.2 37.1 Example 5 426.4 531.8 190.6 38.5 Comparative Example 1 415.6 523.0 752.4 24.2 Comparative Example 2 367.1 455.8 213.4 29.5

[0077] From the test results in Table 1, it can be seen that the composite materials obtained in Examples 1 to 5 all have excellent mechanical properties and low-toxic flame retardant properties. The limiting oxygen index can prove that the low-toxic flame retardant composite materials in Examples 1 to 5 can reach the flame retardant or non-flammable grade.

[0078] In contrast, in Comparative Example 1, the vinyl resin was not modified by using a modifier such as cage-type polysiloxane, and the resulting composite material had a high smoke density, a low oxygen index, and was easy to burn. In Comparative Example 2, the proportion of each component in the resin system was adjusted, resulting in a high viscosity of the resin system, which in turn reduced the mechanical properties of the composite material. The smoke density in Comparative Examples 1 and 2 was greater than 200, and the oxygen index was less than 30%, which failed to meet the requirements of the FTP 2010 International Fire Test Procedure Application Rules: "For materials used as bulkheads, linings or ceiling surfaces, the smoke density shall not exceed 200 under any test conditions."

[0079] The low-toxic flame-retardant composite material provided in this embodiment can meet the requirements of fire retardancy and low smoke toxicity in ship cabins, and has excellent marine environment resistance and light weight and high strength performance, which is conducive to achieving the goals of lightweight, low-carbon and environmentally friendly ships. At the same time, the excellent corrosion resistance and weather resistance of the composite material can extend the service life of the corresponding application products, reduce maintenance costs, and is suitable for harsh marine environments.

[0080] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A low-toxic flame-retardant composite material, characterized in that: The low-toxic flame-retardant composite material comprises fibers and a resin system; The resin system comprises a modified vinyl resin, a curing agent and an accelerator.

2. The low-toxic flame-retardant composite material according to claim 1, characterized in that: The resin system comprises, by weight, 90 to 95 parts of modified vinyl resin, 4 to 8.5 parts of curing agent, and 1 to 1.5 parts of accelerator.

3. The low-toxic flame-retardant composite material according to claim 1 or 2, characterized in that: The modified vinyl resin consists of vinyl resin and a modifier, and the modifier is selected from one or two of cage-type polysiloxane and polyphosphoric acid amine.

4. The low-toxic flame-retardant composite material according to claim 3, characterized in that: The weight of the modifier is 15% to 20% of the weight of the modified vinyl resin.

5. The low-toxic flame-retardant composite material according to claim 1 or 2, characterized in that: The curing agent is selected from one or more of methyl ethyl ketone peroxide, acetylacetone peroxide and diketone acrylamide adduct.

6. The low-toxic flame-retardant composite material according to claim 1 or 2, characterized in that: The promoter is selected from one or both of cobalt octoate and cobalt naphthenate.

7. The low-toxic flame-retardant composite material according to claim 1, characterized in that: The viscosity of the resin system is between 150mPa·s~500mPa·s.

8. The low-toxic flame-retardant composite material according to claim 1, characterized in that: The fibers include fiber fabrics, which are woven from one of carbon fiber, glass fiber, basalt fiber, or aramid fiber. The fiber fabric is in the form of plain weave or twill.

9. A method for preparing a low-toxic flame-retardant composite material, characterized in that: The following steps are involved: At room temperature, the vinyl resin reacts with the modifier to obtain a modified vinyl resin; At room temperature, the vinyl resin, curing agent and accelerator react to obtain a resin system; The resin system and the fiber are formed by a vacuum-assisted resin transfer molding process to obtain a low-toxic flame-retardant composite material.

10. The preparation method according to claim 9, characterized in that: The resin system and the fiber are molded by a vacuum-assisted resin transfer molding process, which specifically includes the following steps: Placing the gel coat, the fiber, the release cloth, the guide net and the vacuum bag in the mold in sequence; Vacuuming, after reaching a preset vacuum degree, introducing the resin system through a rubber guide tube; After the resin system is introduced, the composite material is cured; Preferably, the curing temperature of the composite material is between 80° C. and 120° C., and the curing time is between 10 h and 24 h.