Fireproof composite material for ship deck and preparation method thereof

Abstract

The application discloses a kind of fireproof composite material for ship deck and preparation method thereof, the fireproof composite material is by the sandwich structure of upper and lower two skins and the foam core material sandwiched between skin;Skin is fiber reinforced resin, made of raw materials including the following mass fraction: thermoplastic phenolic resin 100 parts, resin curing agent 5~12 parts, diluent 50~120 parts, ceramicizable inorganic filler 10~50 parts, ceramicization auxiliary agent 10~30 parts, flame retardant 0~30 parts, reinforcing fiber 100~150 parts;Resin curing agent is hexamethylene tetramine.The application adopts high carbon residue resin-ceramicizable filler-flame retardant composite modification method, can make composite material deck when encountering fire quickly generate ceramic phase protective layer, block flame spread, while making composite material deck material still maintain certain bearing capacity after fire.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a fire-resistant composite material for ship decks and its preparation method. Background Technology

[0002] Research has already begun on using composite materials to replace traditional metal materials for ship decks. Compared with traditional steel metal materials, resin-based fiber-reinforced composite materials have outstanding advantages such as high specific strength, high specific modulus, and strong corrosion resistance. Composite material decks can effectively reduce the weight of the hull, increase the ship's cargo capacity or reduce fuel consumption and carbon emissions, while also lowering the ship's center of gravity, making navigation safer.

[0003] For example, patent document CN117104391A discloses a frame structure for the upper vehicle deck of an automobile transport ship, which uses composite materials as cover plates to effectively reduce the weight of the upper deck and lower the center of gravity. However, this patent does not involve research on composite materials.

[0004] Patent document CN114163166A discloses a lightweight and environmentally friendly deck dressing and its preparation method. Each part of the dressing includes: 12-16 parts of epoxy resin, 54-60 parts of filler aggregate, 26-30 parts of pre-made powder, 9-12 parts of nitrogen and phosphorus series flame retardants, 2-6 parts of flame retardant synergists, 8-10 parts of polyurethane, 3-6 parts of cholesterol, 5-13 parts of isopropyl acetone, and 34-68 parts of sound-absorbing agent. This deck dressing can effectively improve the absorption effect of ultraviolet rays on the ship deck and also help the deck achieve sound absorption function.

[0005] Patent document CN112874026A discloses a method for preparing a fireproof deck for ships, comprising an inner fireproof bulkhead, an outer fireproof bulkhead, reinforcing strips, and a deck layer. The inner fireproof bulkhead is made of 1.2-2mm glass fiber and thermoplastic resin, with a glass fiber to thermoplastic resin mass ratio of 1-10:50. The outer fireproof bulkhead comprises the following components by mass: 30-50 parts polyether, 50-60 parts polyester, 10-18 parts JTM polyether, 2-7 parts silicone oil, 1.9-2.3 parts catalyst, 7-9 parts triethanolamine, 3-10 parts water, and 43-53 parts flame retardant. The reinforcing strips are made of 2.5-4mm glass fiber and thermoplastic resin, with a glass fiber to thermoplastic resin mass ratio of 10:50-80. However, this deck structure is relatively complex.

[0006] Patent document CN207549618U discloses a lightweight, impact-resistant composite sandwich structure, including an outer panel, an inner panel, and a foam sandwich structure between them; wherein, the outer panel is a thermosetting resin panel reinforced with ultra-high molecular weight polyethylene fiber / carbon fiber hybrid woven fabric; and the inner panel is a thermoplastic resin panel reinforced with continuous glass fiber. However, this document does not disclose the composition formulation of the composite material, so the properties of the composite material itself cannot be known.

[0007] Current research on composite material decks for ships mainly focuses on structure and strength. For example, the literature [Su Jialun. Research on the test and assessment method of the structural strength of sandwich composite material decks [D]. Hubei: Wuhan University of Technology, 2020.] studies the test and assessment method of the structural strength of sandwich composite material decks. However, compared with steel decks, composite material decks are more flammable. If the deck does not have good fire resistance and flame retardant properties in the event of a fire, it will cause serious loss of life and property. In particular, PCTC ships carrying new energy vehicles have higher requirements for the fire resistance and flame retardant properties of the deck because the probability of fire from new energy vehicle batteries during transportation is higher than that of traditional fuel vehicles.

[0008] However, the flame retardancy of polymer composites depends on the addition of flame retardant fillers, but a high proportion of flame retardant fillers will reduce the strength and mechanical properties of the composites, resulting in a situation where high strength and high flame retardancy of polymer composites for decks cannot be achieved at the same time.

[0009] Some researchers have used ceramics to improve the flame retardancy of composite materials used in decking. For example, patent document CN105778700A discloses a phenolic alkyd primer for ship decking and its preparation method. The raw materials include: phenolic resin, alkyd resin, terpene resin, ceramic micro powder, petroleum asphalt, gypsum powder, asbestos powder, nano aluminum powder, rare earth elements, etc. However, the product in this document is a spray primer. Summary of the Invention

[0010] The purpose of this invention is to provide a fire-resistant composite material for ship decks and its preparation method. This fire-resistant composite material has high strength, high fire-retardant properties and high performance retention rate after flame burning, so as to solve the problem that high strength and high flame retardancy cannot be achieved at the same time in the prior art.

[0011] To achieve the above objectives, the technical solution of the present invention is as follows: The present invention provides a fireproof composite material for ship decks, characterized in that it comprises a sandwich structure consisting of upper and lower skin layers and a foam core material sandwiched between the skin layers. The skin is a fiber-reinforced resin, made from the following raw materials in parts by weight: 100 parts thermoplastic phenolic resin, 5-12 parts resin curing agent, 50-120 parts diluent, 10-50 parts ceramizable inorganic filler, 10-30 parts ceramization additive, 0-30 parts flame retardant, and 100-150 parts reinforcing fiber; the resin curing agent is hexamethylenetetramine. The thermoplastic phenolic resin is a thermoplastic phenolic resin with a viscosity of 8000-15000 cP at 25℃, such as PF5465 produced by Jinan Shengquan Group Co., Ltd., PF8522 produced by Shandong Laiwu Runda Chemical Co., Ltd., and 2123 phenolic resin produced by Wuxi Xinyehao Chemical Co., Ltd. The diluent is ethanol and / or acetone, preferably ethanol; The ceramizable inorganic filler is one or more of kaolin, montmorillonite, mica, and talc, with a particle size of 0.05 to 20 μm; preferably one or more of kaolin, montmorillonite, and mica, with a preferred particle size of 1 to 8 μm. It has high ceramization reactivity and high mechanical properties. The ceramizable inorganic filler can form a ceramic barrier layer when exposed to fire, thus preventing flame spread. The ceramicizing agent is one or more of boron oxide, zinc borate, and low-melting-point glass powder with an initial melting temperature of 300-800°C, with a particle size of 1-20 μm; preferably, it is boron oxide or / and low-melting-point glass powder with an initial melting temperature of 400-600°C, and preferably has a particle size of 1-5 μm; the ceramicizing agent has a lower melting temperature, which can accelerate the ceramicizing reaction process and more effectively form a ceramic protective layer; The flame retardant is one or more of aluminum hydroxide, microencapsulated red phosphorus (MRP), organophosphorus flame retardants (such as triphenyl phosphate, bisphenol A bis(diphenyl phosphate) etc.), and DOPO flame retardant (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), preferably one or more of aluminum hydroxide and organophosphorus flame retardants; The reinforcing fiber is one or more of glass fiber cloth and basalt fiber cloth, which has excellent mechanical strength and fire resistance.

[0012] Preferably, the foam core is made of polyvinyl chloride (PVC) foam, polyurethane (PUR) foam, or polyethylene terephthalate (PET) foam, with a density of 50–200 kg / m³. 3 The core thickness is 10-150mm.

[0013] More preferably, the foam core is made of a material with a density of 80–160 kg / m³. 3 The polyethylene terephthalate (PET) foam has a core thickness of 30-60mm and possesses strong mechanical properties and high-temperature resistance.

[0014] The method for preparing the fire-resistant composite material for ship decks according to the present invention is characterized by comprising the following steps: S1, the thermoplastic phenolic resin, diluent and resin curing agent are mixed and stirred until clear and transparent to obtain a resin solution; S2, the ceramicizable inorganic filler, ceramicizable additive and flame retardant are added to the resin solution and stirred evenly to obtain a modified resin solution; S3, The modified resin solution is evenly coated onto the fiber cloth made of the reinforcing fiber and dried to obtain a prepreg; S4, cut the foam core and the prepreg to the specified size, and lay them on the mold in the order of prepreg-core material-prepreg to obtain the profile; S5. After sealing the profile with a vacuum bag, a vacuum is drawn and the vacuum degree is maintained above -98kPa. The profile under negative pressure is placed in a curing oven and heated to a temperature of 120℃~160℃ for 2~5 hours. After cooling, the fireproof composite material for ship decks is obtained.

[0015] Compared with the prior art, the present invention adopts a sandwich structure composed of fiber-reinforced resin matrix composite material and plastic foam, and adds ceramizable inorganic fillers and additives to the resin. The advantage is that the composite modification method of high residual carbon resin-ceramizable filler-flame retardant can enable the composite deck to quickly form a ceramic phase protective layer when exposed to fire, which can block the spread of flames, while the composite deck material still maintains a certain load-bearing capacity after a fire. Detailed Implementation

[0016] Those skilled in the art should recognize that this embodiment is only used to illustrate the present invention and is not intended to limit the present invention. Any changes or modifications to the embodiment within the scope of the present invention are within the scope of the claims of the present invention.

[0017] Example 1 A fire-resistant composite material for ship decks, the preparation method of which is as follows: S1. Mix 100 parts (by weight, the same below) of thermoplastic phenolic resin (PF5465 from Jinan Shengquan, with a viscosity of 9000 cP at 25℃), 100 parts of diluent (ethanol) and 7.5 parts of resin curing agent (hexamethylenetetramine), and stir until clear and transparent to obtain a resin solution. S2, add 20 parts of kaolin, 10 parts of low melting point glass powder (LX560 from Anmi Micro-Nano New Materials Co., Ltd.) and 15 parts of flame retardant aluminum hydroxide to the resin solution and stir evenly to obtain a modified resin solution. S3, the modified resin solution is evenly coated onto 120 parts of glass fiber reinforced fiber cloth and dried at room temperature to obtain prepreg; S4: A density of 100 kg / m³ 3 PET foam core and prepreg with a thickness of 40mm are cut to the specified size and laid on the mold in the order of 5 layers of prepreg - 1 layer of core material - 5 layers of prepreg to obtain the profile. S5: Seal the profile with a vacuum bag and adhesive strip, draw a vacuum, and maintain the vacuum degree above -98 kPa; put the profile under negative pressure into a curing oven, heat it to 150℃ and cure it for 2 hours, take it out and cool it to obtain a fireproof composite material for ship decks.

[0018] Example 2 The difference between Example 2 and Example 1 is that 12 parts of organophosphorus flame retardant (Bisphenol A bis(diphenyl phosphate) produced by Dongguan Daer Chemical Co., Ltd., brand name Doher-6206) are added in step S2; the rest is the same as in Example 1.

[0019] Comparative Example 1 The difference between Comparative Example 1 and Examples 1-2 is that no flame retardant is added in step S2; otherwise, it is the same as Example 1.

[0020] Example 3 The difference between Example 3 and Example 1 is that in step S2, 20 parts of kaolin, 10 parts of mica and 10 parts of boron oxide are added to the resin solution and stirred evenly to obtain a modified resin solution; the rest is the same as in Example 1.

[0021] Example 4 A fire-resistant composite material for ship decks, the preparation method of which is as follows: S1. Mix 100 parts of thermoplastic phenolic resin (PF5465 from Jinan Shengquan), 80 parts of diluent (acetone) and 8 parts of resin curing agent (hexamethylenetetramine), and stir until clear and transparent to obtain a resin solution. S2, add 10 parts of kaolin, 10 parts of low melting point glass powder (LX560 from Anmi Micro-Nano New Materials Co., Ltd.) and 10 parts of organophosphorus flame retardant (Bisphenol A bis(diphenyl phosphate) of Doher-6206 from Dongguan Daer Chemical Co., Ltd.) to the resin solution and stir evenly to obtain the modified resin solution. S3, the modified resin solution is evenly coated onto 120 parts of glass fiber reinforced fiber cloth and dried at room temperature to obtain prepreg; S4: A density of 100 kg / m³ 3 PET foam core and prepreg with a thickness of 40mm are cut to the specified size and laid on the mold in the order of 5 layers of prepreg - 1 layer of core material - 5 layers of prepreg to obtain the profile. S5: Seal the profile with a vacuum bag and adhesive strip, draw a vacuum, and maintain the vacuum degree above -98 kPa; put the profile under negative pressure into a curing oven, heat it to 150℃ and cure it for 2 hours, take it out and cool it to obtain a fireproof composite material for ship decks.

[0022] Example 5 A fire-resistant composite material for ship decks, the preparation method of which is as follows: S1. Mix 100 parts of thermoplastic phenolic resin (2123 phenolic resin from Wuxi Xinyehao Chemical Co., Ltd.), 100 parts of diluent (ethanol) and 7.5 parts of resin curing agent (hexamethylenetetramine), and stir until clear and transparent to obtain a resin solution. S2, add 20 parts of kaolin, 10 parts of boron nitride, 10 parts of low melting point glass powder (LX680 from Anmi Micro-Nano New Materials Co., Ltd.) and 12 parts of flame retardant (Triphenyl phosphate of Hi-EP218 produced by Jiangsu Xibolai Industrial Co., Ltd.) to the resin solution and stir evenly to obtain the modified resin solution. S3, the modified resin solution is evenly coated onto 120 parts of glass fiber reinforced fiber cloth and dried at room temperature to obtain prepreg; S4: A density of 120 kg / m³ 3 PET foam core and prepreg with a thickness of 30mm are cut to the specified size and laid on the mold in the order of 5 layers of prepreg - 1 layer of core material - 5 layers of prepreg to obtain the profile; S5: Seal the profile with a vacuum bag and adhesive strip, draw a vacuum, and maintain the vacuum degree above -98 kPa; put the profile under negative pressure into a curing oven, heat it to 150℃ and cure it for 2 hours, take it out and cool it to obtain a fireproof composite material for ship decks.

[0023] Example 6 A fire-resistant composite material for ship decks, the preparation method of which is as follows: S1. Mix 100 parts of thermoplastic phenolic resin (PF8522 from Shandong Laiwu Runda Chemical Co., Ltd., with a viscosity of 11000 cP at 25℃), 80 parts of diluent (ethanol), and 8 parts of resin curing agent (hexamethylenetetramine) and stir until clear and transparent to obtain a resin solution. S2, add 30 parts of montmorillonite, 15 parts of low melting point glass powder (LX560 from Anmi Micro-Nano New Materials Co., Ltd.) and 12 parts of flame retardant (Bisphenol A bis(diphenyl phosphate) of the brand Doher-6206 produced by Dongguan Daer Chemical Co., Ltd.) to the resin solution and stir evenly to obtain the modified resin solution. S3, the modified resin solution is evenly coated onto 100 parts of glass fiber reinforced fiber cloth and dried at room temperature to obtain prepreg; S4: A density of 100 kg / m³ 3 PET foam core and prepreg with a thickness of 40mm are cut to the specified size and laid on the mold in the order of 5 layers of prepreg - 1 layer of core material - 5 layers of prepreg to obtain the profile. S5: Seal the profile with a vacuum bag and adhesive strip, draw a vacuum, and maintain the vacuum degree above -98 kPa; put the profile under negative pressure into a curing oven, heat it to 150℃ and cure it for 2 hours, take it out and cool it to obtain a fireproof composite material for ship decks.

[0024] Test Experiment Example Currently, the decks of large PCTC ships or ro-ro passenger ships are all made of metal. Globally, only one PCTC ship in Europe has researched and applied composite material decks. There are no domestically produced ships with composite material decks, nor is there any domestic experience in using composite material decks on ships. Therefore, there are no specific requirements for the design (structure, fire resistance, weather resistance, etc.) of composite material decks. This invention focuses on key properties of the material, such as oxygen index, flexural strength, and flexural strength after simulated fire, as indicators, emphasizing the fire resistance and load-bearing capacity of the deck.

[0025] The fire-resistant composite materials for ship decks described in Examples 1-6 were tested. The oxygen index of the skin material was tested according to GB / T 8924-2005. The flexural strength of the skin was tested according to ISO 178-2010. A butane torch was used to conduct a flame test on the skin material, with the torch flame perpendicular to the skin material and the flame tip 30 mm away from the skin material, for a continuous flame exposure of 10 minutes. The flexural strength of the treated skin material samples was then tested according to ISO 178-2010. The test results are shown in Table 1. Table 1 Test results of Examples 1-6 and Comparative Example 1 As can be seen from Table 1, Examples 1 to 6 all have a high oxygen index and excellent flame retardant properties; they also have high flexural strength and strength retention rate after flame treatment.

[0026] In Examples 1 and 2, a flame retardant was added compared to Comparative Example 1, which can effectively improve the flame retardant efficiency and effectively prevent the flame from eroding the interior during flame treatment, thus resulting in a higher strength retention rate. However, the initial bending strength was slightly reduced due to the addition of liquid-added organophosphorus flame retardant.

[0027] In Example 3, the ceramizable inorganic filler uses a blend of kaolin and mica, two fillers with different ceramic-forming temperatures, enabling the material to form a ceramic protective layer over a wider temperature range. Compared to Example 1, using boron oxide as a ceramic-forming aid, which has a lower melting temperature and higher efficiency than low-melting-point glass powder, accelerates the ceramization process of the material. Upon exposure to flame and high temperatures, it rapidly generates a molten liquid phase, allowing the ceramizable inorganic filler to achieve ceramization more quickly, protecting the material and preventing flame propagation. Therefore, its strength retention rate after flame treatment is significantly improved.

[0028] Example 4 shows that the addition of flame retardant results in a higher oxygen index. Although the strength retention rate is lower due to the reduction in filler content, it still meets the requirements.

[0029] The key factors affecting the product of this invention are the combined use of ceramizable fillers, ceramizing additives, and flame retardants. Ceramizable composite material technology is commonly used in the aerospace field. When hypersonic vehicles withstand high temperatures of 1000–2000°C and flame erosion, the composite material can maintain its shape and a certain mechanical strength. However, the ceramizable fillers and ceramizing additives used in the aerospace field are all expensive materials; and hypersonic vehicles do not need to consider flame retardancy under high-speed atmospheric erosion. When a ship deck is affected by a fire, the environment is not as harsh as that of an aircraft. Therefore, this invention uses inexpensive silicate mineral materials as ceramizable fillers and ceramizing additives, combined with flame retardants, which can effectively achieve the effects of flame retardancy and preventing the spread of flames.

[0030] If only ceramizable fillers and ceramization additives are added without flame retardants, the flame generated by the combustion of the resin matrix cannot be reduced, posing a threat to the safety of cargo and personnel on board. If only flame retardants are added without ceramizable fillers and ceramization additives, the heat generated by the fire will cause the composite material structure to collapse, making it unable to maintain a certain strength and causing more serious consequences such as deck collapse. As can be seen from Examples 1 to 6, the present invention uses a composite modification method of high residual carbon resin-ceramizable filler-flame retardant, which enables the composite deck to quickly form a ceramic phase protective layer when exposed to fire, blocking the spread of flames, while allowing the composite deck material to maintain a certain load-bearing capacity after a fire.

Claims

1. A fire-resistant composite material for ship decks, characterized in that, A sandwich structure consisting of upper and lower skin layers and a plastic foam core material sandwiched between the skin layers; The skin is a fiber-reinforced resin, made from the following raw materials in parts by weight: 100 parts of thermoplastic phenolic resin with a viscosity of 8000-15000 cP at 25°C, 5-12 parts of hexamethylenetetramine as a resin curing agent, 50-120 parts of diluent, 10-50 parts of ceramizable inorganic filler, 10-30 parts of ceramization additive, 10-30 parts of flame retardant, and 100-150 parts of reinforcing fiber; The ceramizable inorganic filler is one or more of kaolin, montmorillonite, and mica, with a particle size of 0.05–20 μm; the ceramization aid is one or more of boron oxide, zinc borate, and low-melting-point glass powder with an initial melting temperature of 300–800℃, with a particle size of 1–20 μm; the reinforcing fiber is one or more of glass fiber cloth and basalt fiber cloth.

2. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The diluent is ethanol and / or acetone.

3. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The ceramizable inorganic filler is one or more of kaolin, montmorillonite, and mica, with a particle size of 1–8 μm.

4. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The ceramicizing agent is boron oxide and / or low-melting-point glass powder with an initial melting temperature of 400-600℃ and a particle size of 1-5μm.

5. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The flame retardant is one or more of aluminum hydroxide, microencapsulated red phosphorus, organophosphorus flame retardant, and DOPO flame retardant.

6. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The flame retardant is one or more of aluminum hydroxide and organophosphorus flame retardants.

7. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The plastic foam core material is made of polyvinyl chloride foam, polyurethane foam, or polyethylene terephthalate foam, with a density of 50–200 kg / m³. 3 The thickness is 10-150mm.

8. The fire-resistant composite material for ship decks according to claim 1, characterized in that, The plastic foam core material has a density of 80–160 kg / m³. 3 The foam is made of polyethylene terephthalate with a core thickness of 30-60 mm.

9. The method for preparing fire-resistant composite material for ship decks according to any one of claims 1 to 8, characterized in that, Includes the following steps: S1, the thermoplastic phenolic resin, diluent and resin curing agent are mixed and stirred until clear and transparent to obtain a resin solution; S2, the ceramicizable inorganic filler, ceramicizable additive and flame retardant are added to the resin solution and stirred evenly to obtain a modified resin solution; S3, The modified resin solution is evenly coated onto the fiber cloth made of the reinforcing fiber and dried to obtain a prepreg; S4, cut the plastic foam core material and the prepreg to the specified size, and lay them on the mold in the order of prepreg-plastic foam core material-prepreg to obtain the profile; S5. After sealing the profile with a vacuum bag, a vacuum is drawn and the vacuum degree is maintained above -98kPa. The profile under negative pressure is placed in a curing oven and heated to a temperature of 120℃~160℃ for 2~5 hours. After cooling, the fireproof composite material for ship decks is obtained.

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