Composition for preparing flame-retardant material, preparation method of composition, flame-retardant material and preparation method and application of flame-retardant material

Abstract

The invention relates to the technical field of aerogel flame-retardant materials, and discloses a composition for preparing a flame-retardant material, a preparation method of the composition, the flame-retardant material and a preparation method and application of the flame-retardant material, and the composition for preparing the flame-retardant material comprises resin, metal oxide doped silicon dioxide aerogel and a fiber material; based on the total weight of the composition, the content of the resin is 18-27 wt%, the content of the metal oxide doped silicon dioxide aerogel is 0.1-1 wt%, and the content of the fiber material is 72-81 wt%. The flame-retardant material prepared from the composition has relatively good mechanical properties and also has excellent flame retardance.

Description

Technical Field

[0001] The invention relates to the technical field of aerogel flame retardant materials, and in particular to a composition for preparing a flame retardant material and a preparation method thereof, and a flame retardant material and a preparation method and application thereof. Background Art

[0002] Wind turbine blades are the most important components for capturing wind energy during wind power generation. They work in all-weather conditions at high altitudes all year round, bearing heavy loads and operating in harsh environments. In order to improve power generation efficiency, wind turbines are often located in areas with harsh climates and sparse populations. Once a blade is struck by lightning and catches fire, it will not only bring expensive repair costs, but also cause serious losses in power generation. The reliability of its quality is the decisive factor in ensuring the safe and efficient operation of the unit. The main beam is the main load-bearing structure in the wind turbine blade, and its flame retardant properties determine the stability of the blade in an emergency.

[0003] The manufacturing of wind turbine blade main beams is mainly based on pultrusion technology. In the pultrusion process, the pultrusion process of composite materials can be improved by adding functional fillers. Fillers can not only improve the pultrusion process, ensure the smooth progress of the composite material pultrusion process, and ensure the stability of the composite material performance, but also improve the performance of the resin matrix and improve the dynamic and static mechanical properties of the composite material. However, the existing fillers cannot take into account the mechanical properties and flame retardant properties of the wind turbine blade main beam. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem that the flame retardant properties and mechanical properties of flame retardant materials in the prior art are poor and it is difficult to take both properties into consideration, and to provide a composition for preparing a flame retardant material and a preparation method thereof, a flame retardant material and a preparation method and application thereof, wherein the composition contains metal oxide-doped silica aerogel, so that the flame retardant material prepared by the composition has good mechanical properties and excellent flame retardant properties.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a composition for preparing a flame retardant material, which comprises a resin, a metal oxide-doped silica aerogel and a fiber material;

[0006] Based on the total weight of the composition, the content of the resin is 18-27 wt %, the content of the metal oxide-doped silica aerogel is 0.1 wt %-1 wt %, and the content of the fiber material is 72-81 wt %.

[0007] A second aspect of the present invention provides a flame retardant material, wherein the flame retardant material is prepared from the above-mentioned composition for preparing a flame retardant material.

[0008] A third aspect of the present invention provides a method for preparing a flame retardant material, wherein the flame retardant material is obtained by mixing the components of the composition for preparing the flame retardant material and then heating and molding the mixture.

[0009] A fourth aspect of the present invention provides a composition for preparing a flame retardant material or an application of the flame retardant material in a main beam of a wind turbine blade.

[0010] Through the above technical scheme, a composition for preparing a flame retardant material and a preparation method thereof, and a flame retardant material and a preparation method and application thereof provided by the present invention have the following beneficial effects.

[0011] In the present invention, the composition for preparing the flame retardant material contains metal oxide doped with silica aerogel; the metal oxide forms a metal oxide coating on the surface of the resin and fiber matrix, which has a physical barrier effect to protect the lower matrix from further combustion and can effectively absorb smoke and gas. When the amount of each component in the composition is controlled to meet the above range, the flame retardant material prepared has not only good mechanical properties, but also excellent flame retardant properties.

[0012] Furthermore, the flame retardant material of the present invention exhibits good mechanical properties and excellent flame retardant properties, and can meet the stability requirements of the main beam of the wind turbine blade in emergency situations, such as combustion situations. DETAILED DESCRIPTION

[0013] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0014] The first aspect of the present invention provides a composition for preparing a flame retardant material, which comprises a resin, a metal oxide-doped silica aerogel and a fiber material;

[0015] Based on the total weight of the composition, the content of the resin is 18-27 wt %, the content of the metal oxide-doped silica aerogel is 0.1 wt %-1 wt %, and the content of the fiber material is 72-81 wt %.

[0016] In the present invention, the composition for preparing the flame retardant material contains metal oxide doped with silica aerogel; the metal oxide forms a coating on the surface of the resin and the fiber matrix, which has a physical barrier function to protect the lower matrix from further combustion and can effectively absorb smoke and gas. When the amount of each component in the composition is controlled to meet the above range, the flame retardant material prepared not only has good mechanical properties, but also has excellent flame retardant properties.

[0017] In the present invention, the total content of the resin, the metal oxide-doped silica aerogel and the fiber material is 100 wt%.

[0018] Further, based on the total weight of the composition, the content of the resin is 19.5-25.75wt%, the content of the metal oxide-doped silica aerogel is 0.25wt%-0.5wt%, and the content of the fiber material is 74-80wt%.

[0019] According to the present invention, the metal oxide doped in the metal oxide-doped silica aerogel is selected from at least one of iron oxide, cobalt oxide and nickel oxide.

[0020] In the present invention, when the silicon dioxide aerogel is doped with the above metal oxides, the obtained flame retardant material has better mechanical properties and flame retardant properties.

[0021] According to the present invention, in the metal oxide-doped silica aerogel, the content of the metal oxide doping is 10wt%-90wt%.

[0022] In the present invention, when the content of the metal oxide doping meets the above range, the prepared flame retardant material has better mechanical properties and flame retardant properties.

[0023] Furthermore, in the metal oxide-doped silica aerogel, the content of the metal oxide doping is 50 wt%-80 wt% calculated as oxide.

[0024] According to the present invention, the average particle size of the metal oxide-doped silica aerogel is 5-100 μm.

[0025] In the present invention, when the average particle size of the metal oxide-doped silica aerogel meets the above range, the prepared flame retardant material has better flame retardant properties.

[0026] Furthermore, the metal oxide-doped silica aerogel has an average particle size of 40-50 μm.

[0027] According to the present invention, the resin is an epoxy resin.

[0028] According to the present invention, the fiber material is selected from glass fiber and / or carbon fiber.

[0029] In the present invention, the source of the metal oxide-doped silica aerogel is not particularly limited and can be obtained commercially or prepared according to the prior art.

[0030] According to a preferred embodiment of the present invention, the method for preparing the metal oxide-doped silica aerogel comprises:

[0031] (1) impregnating the silica aerogel with a metal salt solution to obtain a metal ion-impregnated silica aerogel;

[0032] (2) drying, calcining and grinding the metal ion-impregnated silica aerogel to obtain the metal oxide-doped silica aerogel.

[0033] According to a preferred embodiment of the present invention, the metal salt is selected from at least one of iron nitrate, cobalt nitrate and nickel nitrate.

[0034] According to a preferred embodiment of the present invention, the concentration of the metal salt solution is 0.01 wt%-10 wt%.

[0035] Furthermore, the concentration of the metal salt solution is 5wt%-9wt%.

[0036] In the present invention, the solvent of the metal salt solution is selected from at least one of water, methanol and ethanol.

[0037] In the present invention, there is no particular limitation on the impregnation method, for example, an equal volume impregnation method is used.

[0038] In the present invention, there is no particular limitation on the source of the silica aerogel, and the silica aerogel can be obtained commercially or prepared by existing methods.

[0039] According to a preferred embodiment of the present invention, in step (2), the drying temperature is 40-120° C., and the drying time is 1-24 h.

[0040] Furthermore, the drying temperature is 60-80° C., and the drying time is 5-8 hours.

[0041] According to a preferred embodiment of the present invention, the burning temperature is 300-600° C., and the burning time is 1-24 hours.

[0042] Furthermore, the calcination temperature is 450-500°C, and the calcination time is 4-8h.

[0043] A second aspect of the present invention provides a flame retardant material, wherein the flame retardant material is prepared from the above-mentioned composition for preparing a flame retardant material.

[0044] In the present invention, when the flame retardant material is in a burning state, the doped metal oxide can form a coating on the surface of the resin and the fiber matrix, which acts as a physical barrier to protect the underlying matrix from further combustion and can effectively absorb smoke and gas, so that the flame retardant material not only has good mechanical properties, but also has excellent flame retardant properties.

[0045] According to the present invention, the tensile strength of the flame retardant material is greater than or equal to 2000 MPa.

[0046] Furthermore, the tensile strength of the flame retardant material is greater than or equal to 2300 MPa.

[0047] According to the present invention, the flame retardant material has a UL-94 rating of V-2, V-1 or V-0.

[0048] Furthermore, the flame retardant material has a UL-94 rating of V-1 or V-0.

[0049] According to the present invention, the flame retardant material has a limited oxygen index greater than or equal to 15%.

[0050] Furthermore, the flame retardant material has an oxygen limiting index greater than or equal to 30%.

[0051] In the present invention, there is no special requirement for the size of the flame retardant material, for example, it can be 100-1500mm*10-150mm*2-10mm.

[0052] A third aspect of the present invention provides a method for preparing a flame retardant material, wherein the flame retardant material is obtained by mixing the components of the composition for preparing the flame retardant material and then heating and molding the mixture.

[0053] According to the present invention, the temperature of the heating molding is 140-200°C.

[0054] According to the present invention, the heating and forming speed is 30-50 cm / min.

[0055] According to a preferred embodiment of the present invention, a flame retardant material is prepared by a pultrusion method, which comprises: mixing a metal oxide-doped silica aerogel with a resin, and then mixing it with a fiber material for pultrusion. Preferably, the temperature of the first zone of the pultruder is 140-160°C, the temperature of the second zone is 150-180°C, and the temperature of the third zone is 150-200°C. Preferably, the pultrusion speed is 30-50 cm / min.

[0056] In the present invention, the temperature of the first zone, the temperature of the second zone and the temperature of the third zone are in an increasing trend.

[0057] A fourth aspect of the present invention provides a composition for preparing a flame retardant material or an application of the flame retardant material in a main beam of a wind turbine blade.

[0058] The flame retardant material of the present invention exhibits good mechanical properties and excellent flame retardant properties, and can meet the stability requirements of the main beam of the wind turbine blade in emergency situations, such as combustion situations.

[0059] The present invention will be described in detail below through examples.

[0060] In the following examples, the limiting oxygen index (LOI) of the aerogel was tested using a limiting oxygen index tester according to the ASTM D2863-2009 standard. The aerogel sample was placed in a combustion chamber, and the oxygen content in the atmosphere was adjusted to find the minimum oxygen concentration that can maintain combustion. The sample size was 130*10*4mm. Each sample was tested 3 times and the average value was taken.

[0061] UL-94 The aerogel samples were subjected to vertical combustion (UL-94) test according to ASTM D3801 standard, sample size: 130*10*4mm, each test was performed 3 times, and the average value was taken.

[0062] The tensile strength was tested using a YF-900 computer tensile testing machine. At least three parallel samples were tested for each sample and the average value was taken. The test speed was 2 mm / min.

[0063] The metal oxide doping content was measured by ICP test.

[0064] The average particle sizes of metal oxide-doped silica aerogel and silica aerogel are measured by a grinding and sieving method.

[0065] In the following preparation examples, embodiments and comparative examples, the epoxy resin is a commercial product of OLIN with a brand name of 550E. The silica aerogel is a commercial product of Zhongke Runzi Company with a brand name of Gel HK ultra-low thermal insulation particles. The carbon fiber is 48K carbon fiber.

[0066] Unless otherwise specified, the equipment, materials, etc. used in the following preparation examples, embodiments and comparative examples can be obtained from public commercial sources.

[0067] Preparation Example 1

[0068] Preparation of metal oxide doped silica aerogel: 7.41 g of cobalt nitrate and 100 mL of water were mixed into a solution (concentration of 6.9 wt%), and the silica aerogel was impregnated with equal volumes. The impregnated aerogel was dried at 60 ° C for 6 h, and then transferred to a muffle furnace and calcined at 480 ° C for 6 h. After grinding and sieving, metal oxide doped silica aerogel Q1 was obtained. The relevant parameters of metal oxide doped silica aerogel Q1 are shown in Table 1.

[0069] Preparation Example 2

[0070] Preparation of metal oxide doped silica aerogel: 9.91g nickel nitrate and 100mL water were prepared into a solution (concentration of 9.02wt%), and the silica aerogel was impregnated with equal volume. The impregnated aerogel was dried at 60°C for 6h, and then transferred to a muffle furnace and calcined at 480°C for 6h. After grinding and sieving, metal oxide doped silica aerogel Q1 was obtained. The relevant parameters of metal oxide doped silica aerogel Q1 are shown in Table 1.

[0071] Preparation Example 3

[0072] Preparation of metal oxide doped silica aerogel: 3.46g of ferric nitrate and 100mL of water were prepared into a solution (concentration of 3.34wt%), and the silica aerogel was impregnated with equal volume. The impregnated aerogel was dried at 60°C for 6h, and then transferred to a muffle furnace and calcined at 480°C for 6h. After grinding and sieving, metal oxide doped silica aerogel Q3 was obtained. The relevant parameters of metal oxide doped silica aerogel Q3 are shown in Table 1.

[0073] Preparation Example 4

[0074] Preparation of metal oxide doped silica aerogel: 3.01 g of cobalt nitrate was mixed with 100 mL of methanol to prepare a solution (concentration of 2.92 wt%), and the silica aerogel was impregnated with equal volume. The impregnated aerogel was dried at 60 ° C for 6 h, and then transferred to a muffle furnace and calcined at 480 ° C for 6 h. After grinding and sieving, metal oxide doped silica aerogel Q4 was obtained. The relevant parameters of metal oxide doped silica aerogel Q4 are shown in Table 1.

[0075] Preparation Example 5

[0076] Preparation of metal oxide doped silica aerogel: 1.98g nickel nitrate and 100mL ethanol were mixed into a solution (concentration of 1.94wt%), and the silica aerogel was impregnated with equal volume. The impregnated aerogel was dried at 60°C for 6h, and then transferred to a muffle furnace and calcined at 480°C for 6h. After grinding and sieving, metal oxide doped silica aerogel Q5 was obtained. The relevant parameters of metal oxide doped silica aerogel Q5 are shown in Table 1.

[0077] Preparation Example 6

[0078] Preparation of metal oxide doped silica aerogel: 4.32g of ferric nitrate was mixed with 100mL of water to make a solution (concentration of 4.14wt%), and the silica aerogel was impregnated with equal volume. The impregnated aerogel was dried at 60°C for 6h, and then transferred to a muffle furnace and calcined at 480°C for 6h. After grinding and sieving, metal oxide doped silica aerogel Q6 was obtained. The relevant parameters of metal oxide doped silica aerogel Q6 are shown in Table 1.

[0079] Preparation Example 7

[0080] Preparation of metal oxide-doped silica aerogel: Metal oxide-doped silica aerogel Q7 was prepared according to the method of Preparation Example 1, except that the metal oxide-doped silica aerogel Q7 with an average particle size of 100 μm was obtained by grinding and sieving. Other parameters are shown in Table 1.

[0081] Preparation Example 8

[0082] Preparation of metal oxide-doped silica aerogel: Metal oxide-doped silica aerogel Q8 was prepared according to the method of Preparation Example 6, except that the metal oxide-doped silica aerogel Q8 with an average particle size of 100 μm was obtained by grinding and sieving. Other parameters are shown in Table 1.

[0083] Table 1

[0084]

[0085] Example 1

[0086] The metal oxide doped silica aerogel Q1 was mixed into the resin and stirred evenly. The resin was poured into the glue tank of the pultruder. The carbon fiber was used to prepare the pultruded sheet. The content of each component is shown in Table 2. The mold specification is 120mm*5mm*900mm. The three-zone temperatures are 155℃, 170℃, and 190℃ respectively. The pultrusion speed is 40cm / min. The flame retardant material A1 was obtained. The performance parameters of the flame retardant material A1 are shown in Table 3.

[0087] Embodiment 2-8

[0088] The flame retardant material was prepared according to the preparation method of Example 1. The contents of the components are shown in Table 2. The performance parameters of the flame retardant material are shown in Table 3.

[0089] Comparative Example 1

[0090] The flame retardant material was prepared according to the preparation method of Example 1, except that the metal oxide-doped silica aerogel Q1 was not added.

[0091] Comparative Example 2

[0092] The flame retardant material was prepared according to the preparation method of Example 1, except that the metal oxide-doped silica aerogel Q1 was replaced with an equal volume of talc.

[0093] Comparative Example 3

[0094] The flame retardant material was prepared according to the preparation method of Example 1, except that the metal oxide-doped silica aerogel Q1 was replaced with an equal volume of silica aerogel.

[0095] Comparative Example 4

[0096] The flame retardant material was prepared according to the preparation method of Example 1, except that the flame retardant material was prepared according to the amount of each component in Table 2.

[0097] Table 2

[0098]

[0099]

[0100] Table 3

[0101] Limiting oxygen index (%) UL-94 Tensile strength(MPa) Example 1 42.3 V-0 2313 Example 2 48.7 V-0 2291 Example 3 34.9 V-1 2340 Example 4 30.3 V-1 2352 Example 5 27.1 V-2 2344 Example 6 38.6 V-0 2319 Example 7 26.5 V-1 2270 Example 8 43.2 V-0 2230 Comparative Example 1 18.2 Fail* 2265 Comparative Example 2 23.3 V-2 2278 Comparative Example 3 25.2 V-2 2283 Comparative Example 4 49.4 V-0 1880

[0102] *Fail refers to failure to meet V-0, V-1 and V-2 ratings in UL-94 testing.

[0103] It can be seen from Table 3 that the comprehensive performance of the flame retardant material of the present invention is better than that of the material prepared in the comparative example. Comparative example 2 is a traditional preparation method for the main beam of a wind turbine blade. Compared with comparative example 2, the tensile strength of the embodiment does not change much, indicating that replacing talc with metal oxide-doped silica aerogel does not reduce the mechanical properties of the flame retardant material.

[0104] The flame retardant material prepared in the embodiment of the present application has a higher limiting oxygen index, indicating that the metal oxide-doped aerogel material has a good flame retardant effect on the composite pultruded sheet. The doped metal oxide decomposes and forms a coating on the surface of the resin and the fiber matrix, which acts as a physical barrier to protect the lower matrix from further combustion and can effectively absorb smoke and gas. In the preferred embodiment, the metal ions doped in the silica aerogel can catalyze the formation of residual carbon, and the carbon layer has a high degree of graphitization and high thermal oxidation resistance, just like a physical shield, inhibiting the diffusion of combustible gases, isolating O2, and delaying further combustion of the internal polymer.

[0105] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A composition for preparing a flame retardant material, characterized in that: Contains resin, metal oxide doped silica aerogel and fiber material; Based on the total weight of the composition, the content of the resin is 18-27 wt %, the content of the metal oxide-doped silica aerogel is 0.1 wt %-1 wt %, and the content of the fiber material is 72-81 wt %.

2. The composition according to claim 1, wherein Based on the total weight of the composition, the content of the resin is 19.5-25.75wt%, the content of the metal oxide-doped silica aerogel is 0.25wt%-0.5wt%, and the content of the fiber material is 74-80wt%; Preferably, the metal oxide doped in the metal oxide-doped silica aerogel is selected from at least one of iron oxide, cobalt oxide and nickel oxide; Preferably, in the metal oxide-doped silica aerogel, the content of the metal oxide doping is 10wt%-90wt%, preferably 50wt%-80wt%; Preferably, the average particle size of the metal oxide-doped silica aerogel is 5-100 μm, preferably 40-50 μm.

3. The composition according to claim 1 or 2, wherein The resin is epoxy resin; Preferably, the fiber material is selected from glass fiber and / or carbon fiber.

4. The composition according to claim 1, wherein The preparation method of the metal oxide-doped silica aerogel comprises: (1) impregnating the silica aerogel with a metal salt solution to obtain a metal ion-impregnated silica aerogel; (2) drying, calcining and grinding the metal ion-impregnated silica aerogel to obtain the metal oxide-doped silica aerogel.

5. The composition according to claim 4, wherein The metal salt is selected from at least one of iron nitrate, cobalt nitrate and nickel nitrate; Preferably, the concentration of the metal salt solution is 0.01 wt%-10 wt%, preferably 5 wt%-9 wt%.

6. The composition according to claim 4 or 5, wherein In step (2), the drying temperature is 40-120° C., preferably 60-80° C.; the drying time is 1-24 hours, preferably 5-8 hours; Preferably, the calcination temperature is 300-600°C, preferably 450-500°C; the calcination time is 1-24h, preferably 4-8h.

7. A flame retardant material, characterized in that: The flame retardant material is prepared from the composition for preparing a flame retardant material according to any one of claims 1 to 6; Preferably, the tensile strength of the flame retardant material is greater than or equal to 2000 MPa, preferably greater than or equal to 2300 MPa; Preferably, the flame retardant material has a UL-94 rating of V-2, V-1 or V-0, preferably V-1 or V-0; Preferably, the flame retardant material has an oxygen limiting index greater than or equal to 15%, preferably greater than or equal to 30%.

8. A method for preparing a flame retardant material, characterized in that: The flame retardant material is obtained by mixing the components of the composition for preparing the flame retardant material according to any one of claims 1 to 6 and then heating and molding the mixture.

9. The preparation method according to claim 8, wherein: The heating temperature is 140-200°C. Preferably, the heating and forming speed is 30-50 cm / min.

10. The composition for preparing a flame retardant material according to any one of claims 1 to 6, or the use of the flame retardant material according to claim 7 in a main beam of a wind turbine blade.

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