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CN-122011671-A - Composite material plate and preparation method and application thereof

CN122011671ACN 122011671 ACN122011671 ACN 122011671ACN-122011671-A

Abstract

The invention provides a composite material plate, a preparation method and application thereof, and relates to the technical field of advanced composite materials. The composite material plate mainly comprises a hybrid resin matrix and a reinforced fiber body, wherein the hybrid resin matrix is mainly prepared from organic silicon resin, phenolic resin, a ceramic precursor polymer, a functional additive and the like, and is mixed with the reinforced fiber body through the design of a ternary hybrid resin matrix, so that the uniformity of extremely high temperature resistance and high structural strength is realized, the prepared composite material plate has ultrahigh fire resistance (1500 ℃ oxygen-acetylene flame 30 min+), high structural strength (tensile strength is not less than 320MPa, bending resistance is not less than 280 MPa) and good process adaptability, and meanwhile, the prepared composite material plate also has lower density, realizes uniformity of light weight and high structural strength, can replace a metal fireproof plate, is suitable for lightweight fireproof structural members such as battery covers and fireproof plates, and has important application value.

Inventors

  • LEI YU
  • He Jinbi
  • LIU XIANHAO
  • JIANG BING

Assignees

  • 海鹰空天材料研究院(苏州)有限责任公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (10)

  1. 1. The composite material plate is characterized by being mainly prepared from a hybrid resin matrix and a reinforced fiber body; wherein, based on the total mass fraction of the raw materials in the hybrid resin matrix as 100%, the hybrid resin matrix comprises the following raw materials in mass fraction: 20-40% of organic silicon resin, 30-50% of phenolic resin, 10-30% of ceramic precursor polymer and 0-5% of functional auxiliary agent.
  2. 2. The composite board according to claim 1, wherein the hybrid resin matrix is a hybrid polymer formed by copolymerizing a silicone resin, a phenolic resin, a ceramic precursor polymer, and a functional additive to form an interpenetrating/semi-interpenetrating network structure; And/or the reinforcing fiber body comprises one or more of a hybrid braid or unidirectional cloth made of at least one of glass fibers, carbon fibers, high silica fibers, basalt fibers, quartz fibers or alumina fibers.
  3. 3. The composite sheet according to claim 1, wherein the silicone resin comprises at least one of phenyl, vinyl, methyl or epoxy containing silicone, or MQ silicone, preferably methyl phenyl silicone, phenyl vinyl silicone, methyl vinyl silicone, epoxy modified silicone or MQ silicone; And/or the phenolic resin comprises at least one of a novolac resin, an allylated phenolic resin, a boron modified phenolic resin or a molybdenum modified phenolic resin; And/or the ceramic precursor polymer comprises at least one of polycarbosilane, polysilazane, or polyborosilazane; And/or the functional auxiliary agent comprises at least one of a condensation accelerator, a leveling agent or a coupling agent; and/or the mass ratio of the hybrid resin matrix to the reinforcing fiber body is (30-45): 55-70.
  4. 4. A composite board as set forth in claim 3, wherein the condensation accelerator comprises at least one of dibutyltin dilaurate, stannous octoate, p-toluenesulfonic acid, triethylamine or cobalt iso-octoate; and/or the leveling agent comprises at least one of BYK-306, BYK-333, TEGO Glide 410 or fluorocarbon leveling agent; and/or the coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyl trimethoxysilane or aluminate coupling agent.
  5. 5. The composite sheet material according to any one of claims 1 to 4, wherein the perforation time of a 1mm thick composite sheet material under an oxy-acetylene flame having a flame temperature of 1500±50 ℃ is not less than 30min; and/or the tensile strength of the composite material plate is more than or equal to 320MPa, and the bending strength is more than or equal to 280MPa; And/or the density of the composite material plate is less than or equal to 2.2 g/cm3.
  6. 6. A method of producing a composite board as claimed in any one of claims 1 to 5, comprising the steps of: (a) Mixing organic silicon resin, phenolic resin, ceramic precursor polymer and optional functional auxiliary agent in proportion, heating and stirring, and reacting to form hybrid resin solution; (b) When the molding is carried out by adopting a compression molding or autoclave process, the reinforced fiber body after surface treatment is immersed in the hybridization resin solution to prepare the prepreg, and then the prepreg is laid in a mold according to the design to be solidified and molded, or, When the RTM technology is adopted for molding, directly layering the dry reinforced fiber body subjected to surface treatment in a mold, and then injecting and introducing a hybrid resin solution into the mold for curing molding; (c) And (3) demolding the molded material obtained after the molding in the step (b), and then carrying out gradient heating post-treatment to obtain the composite material plate.
  7. 7. The method of producing a composite sheet according to claim 6, wherein in the step (a), the reaction is carried out at 60 to 80 ℃ for 2 to 4 hours with stirring; And/or, in step (b), the surface treatment comprises a plasma treatment or a sizing agent treatment.
  8. 8. The method of producing a composite sheet according to claim 6, wherein in the step (b), when the molding is performed by a molding or autoclave process, the pressure is 5 to 15MPa, the temperature is 120 to 180 ℃, and the curing time is 30 to 90 minutes; and/or in the step (b), when the molding is performed by adopting an RTM process, the injection pressure is 0.5-2MPa, the mold temperature is 70-90 ℃, the curing temperature is 120-180 ℃, and the curing time is 60-120min; and/or, in the step (c), the gradient temperature-raising post-treatment includes sequentially performing a first-stage temperature-raising treatment, a second-stage temperature-raising treatment, a third-stage temperature-raising treatment, and a fourth-stage temperature-raising treatment; the first-stage heating treatment is to heat the room temperature to 75-85 ℃ and keep the temperature for 1-2h; The second-stage heating treatment is to heat from the temperature of the first-stage heating treatment to 110-130 ℃ and keep the temperature for 1-2h; the third-stage heating treatment is to heat from the temperature of the second-stage heating treatment to 170-190 ℃ and keep the temperature for 1-2h; The fourth stage heating treatment is to heat up to 240-260 ℃ from the temperature of the third stage heating treatment, and keep the temperature for 1-2h; the temperature rising rate in the temperature rising treatment process of each stage is 1-2 ℃ per minute.
  9. 9. The method of producing a composite sheet according to any one of claims 6 to 8, wherein in the step (c), the step of pyrolysis is further included after the gradient temperature post-treatment and before the composite sheet is obtained; Preferably, the temperature adopted in the pyrolysis treatment is 800-1000 ℃, the heat preservation time is 1-2h, and the atmosphere is inert.
  10. 10. Use of the composite sheet material of any one of claims 1 to 5 or the composite sheet material produced by the production process of any one of claims 6 to 9 in the field of new energy automobiles, aerospace or ship industry.

Description

Composite material plate and preparation method and application thereof Technical Field The invention belongs to the technical field of advanced composite materials, and particularly relates to a composite material plate and a preparation method and application thereof. Background With the development of new energy automobiles, aerospace and high-end equipment manufacturing, the demand for composite materials with light weight, high structural strength and extreme fire resistance is increasingly urgent. In the prior art, although the phenolic resin matrix composite material has certain flame retardance, the long-term use temperature is generally lower than 300 ℃, the phenolic resin matrix composite material is rapidly carbonized and failed under 1500 ℃ flame impact, and the epoxy resin matrix composite material is not resistant to high temperature. Inorganic ceramic-based materials are resistant to high temperatures, but have high brittleness and are difficult to mold into complex members. Most of the existing fireproof plates are metal or inorganic plates, and have high density and poor processability. Chinese patent CN110776487B discloses a quartz fiber reinforced phenolic resin composite that can be used for short periods at 1000 ℃, but is hard to withstand the impact of an oxygen-acetylene flame at 1500 ℃ for more than 30 minutes. CN112694771a proposes a ceramic precursor modified phenolic resin, which improves carbon residue rate, but increases brittleness of the matrix and decreases mechanical properties. CN113736072B adopts carbon fiber reinforced silicone resin, the temperature resistance can reach 1200 ℃, but the tensile strength is less than 300MPa, and the structural bearing requirement is difficult to meet. Therefore, developing a light composite material with ultra-high fire resistance (1500 ℃ oxygen-acetylene flame 30 min+), high structural strength (tensile strength is not less than 320MPa, bending resistance is not less than 280 MPa) and good process adaptability is a current technical problem. In view of this, the present invention has been made. Disclosure of Invention The present invention aims to provide a composite board, a preparation method and application thereof, so as to improve the above problems existing in the prior art. The first object of the invention is to provide a composite board which is mainly made of a hybrid resin matrix and a reinforced fiber body; wherein, based on the total mass fraction of the raw materials in the hybrid resin matrix as 100%, the hybrid resin matrix comprises the following raw materials in mass fraction: 20-40% of organic silicon resin, 30-50% of phenolic resin, 10-30% of ceramic precursor polymer and 0-5% of functional auxiliary agent. Furthermore, on the basis of the technical scheme, the hybrid resin matrix is a hybrid polymer with an interpenetrating/semi-interpenetrating network structure formed by copolymerization reaction of organic silicon resin, phenolic resin, ceramic precursor polymer and functional auxiliary agent; And/or the reinforcing fiber body comprises one or more of a hybrid braid or unidirectional cloth made of at least one of glass fibers, carbon fibers, high silica fibers, basalt fibers, quartz fibers or alumina fibers. Further, on the basis of the above technical solution of the present invention, the silicone resin includes at least one of a phenyl group-containing, vinyl group-containing, methyl group-containing or epoxy group-containing silicone resin, or MQ silicone resin, preferably includes a methylphenyl silicone resin, a phenyl vinyl silicone resin, a methyl vinyl silicone resin, an MQ silicone resin or an epoxy modified silicone resin; And/or the phenolic resin comprises at least one of a novolac resin, an allylated phenolic resin, a boron modified phenolic resin or a molybdenum modified phenolic resin; and/or the ceramic precursor polymer comprises at least one of polycarbosilane, polysilazane, or polyborosilazane. Furthermore, on the basis of the technical scheme of the invention, the mass ratio of the hybrid resin matrix to the reinforced fiber body is (30-45) (55-70); and/or the functional auxiliary agent comprises at least one of a condensation accelerator, a leveling agent or a coupling agent. Further, on the basis of the technical scheme, the condensation accelerator comprises at least one of dibutyl tin dilaurate, stannous octoate, p-toluenesulfonic acid, triethylamine or cobalt iso-octoate; and/or the leveling agent comprises at least one of BYK-306, BYK-333, TEGO Glide 410 or fluorocarbon leveling agent; and/or the coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyl trimethoxysilane or aluminate coupling agent. Furthermore, on the basis of the technical scheme, the hole burning time of the composite material plate with the thickness of 1mm under the oxygen-acetylene