Construction method of thermal insulation material for ship body

Abstract

The invention discloses a thermal insulation material construction method for a ship body, and relates to the technical field of ship body construction, the construction method comprises the following steps: base material surface treatment, primer coating, thermal insulation material installation, flame retardant layer construction and surface treatment; the thermal insulation material is prepared from the following components in parts by weight: 100 to 120 parts of polyether polyol, 110 to 130 parts of diphenylmethane diisocyanate, 8 to 22 parts of modified filler, 5 to 9 parts of petroleum ether, 2 to 6 parts of glycerol, 0.2 to 1 part of dibutyltin dilaurate, 0.5 to 1.5 parts of dimethyl cyclohexylamine and 0.8 to 1.2 parts of pentaerythritol, the thermal insulation material disclosed by the invention integrates excellent thermal insulation performance and excellent flame retardant property, can show excellent dimensional stability and durability in severe environments such as high temperature, high humidity and vibration of ships, and provides a safe and reliable comprehensive thermal insulation solution for the ships.

Description

Technical Field

[0001] The present invention relates to the technical field of ship hull construction, and in particular to a method for constructing a heat-insulating material for a ship hull. Background Art

[0002] Marine insulation materials are a key component in shipbuilding and maintenance, directly impacting ship safety, comfort, and energy efficiency. With the International Maritime Organization (IMO) continuously improving ship fire safety standards and shipowners' increasingly stringent requirements for energy conservation and emission reduction, the research and development and application of high-performance insulation materials and their supporting construction technologies have become particularly important.

[0003] Traditional ship insulation materials primarily include mineral wool, glass wool, and polyurethane foam. These materials are typically applied through mechanical fixing, gluing, or spraying. Mineral wool and glass wool are prone to generating dust during construction, which poses a health hazard to workers. They also have strong water absorption and are prone to aging. Conventional polyurethane foam, while offering excellent insulation properties, lacks flame retardancy and is complex to construct. In the challenging conditions of a ship, such as high temperature, high humidity, and vibration, poor adhesion and improper joint treatment can lead to delamination and shedding of the insulation layer, shortening its service life and increasing safety risks.

[0004] Existing insulation material construction methods are plagued by issues such as irregular surface treatment of the substrate, improper joint management, and poor adaptability in specific areas. This is particularly true in the construction of complex ship structures (such as T-sections, pipeline crossings, and curved surfaces), where inadequate construction methods often lead to partial insulation failure. Furthermore, existing construction methods inadequately seal the free edges of the material, making the insulation susceptible to moisture and deformation. Furthermore, the lack of systematic quality control nodes and environmental constraints makes it difficult to ensure construction quality.

[0005] CN118791694A discloses a thermal insulation polyurethane plastic and a preparation method thereof, wherein the thermal insulation polyurethane plastic contains polyether polyol, 2-fluorophenyl isocyanate, polyethylene glycol, a modified composite filler, a foam stabilizer, a catalyst, a foaming agent, water and an antioxidant; the modified composite filler is a mixture of hollow glass microspheres, magnesium fluorosilicate, ruthenium dioxide and hydromagnesite.

[0006] When it comes to thermal insulation materials, traditional materials often focus solely on either thermal insulation or flame retardancy, failing to meet both requirements simultaneously. Marine environments, in particular, place extremely high demands on insulation materials for flame retardancy, durability, and adaptability, yet existing materials often fall short of practical marine application requirements. Furthermore, issues such as uneven filler dispersion and poor compatibility within insulation materials contribute to unstable performance and a short service life.

[0007] Therefore, developing a high-performance ship insulation material and a systematic and standardized construction method to solve the material performance deficiencies and construction process defects in the existing technology is of great significance to improving ship safety, extending service life and reducing maintenance costs. Summary of the Invention

[0008] In order to address the deficiencies in the prior art, the purpose of the present invention is to provide a method for constructing thermal insulation materials for ship hulls. The thermal insulation material of the present invention combines excellent thermal insulation performance with outstanding flame retardant properties, effectively solving the problems of easy aging and insufficient flame retardancy of traditional thermal insulation materials. It can exhibit excellent dimensional stability and durability in harsh environments such as high temperature, high humidity, and vibration on ships, providing ships with a safe and reliable comprehensive thermal insulation solution.

[0009] In order to achieve the above object, the present invention adopts the following technical solutions:

[0010] A method for constructing a thermal insulation material for a ship hull, comprising the following steps:

[0011] S1. Substrate surface treatment: Clean and roughen the substrate surface;

[0012] S2. Primer coating: Apply adhesive evenly on the contact surface between the substrate and the thermal insulation material;

[0013] S3.Insulation material installation: Press the insulation material onto the substrate surface and treat the seams;

[0014] S4. Flame retardant coating: Lay flame retardant fabric and transition coating on the surface of the insulation material in sequence;

[0015] S5. Surface treatment: Apply multiple layers of putty and topcoat.

[0016] Specifically, step S1 is substrate surface treatment: ensure that the substrate surface has been primed and has passed the inspection of the quality inspection department; use cleaning tools to remove water, oil, paint and impurities on the substrate surface to ensure that the surface is dry; roughen the primer surface to increase the roughness, and wipe the surface residue with a clean rag.

[0017] Specifically, step S2: primer coating: stir the primer until it is uniform, the construction environment temperature is 5-40°C, and the relative humidity is ≤85%; apply the primer evenly in both directions on the substrate surface and the contact surface of the thermal insulation material, with a coating amount of 2.5-3.5 kg / m 2 , ensure that there is no missing paint; if the substrate surface is frosted or the temperature is below 0℃, construction must be suspended.

[0018] Specifically, step S3 is to install the thermal insulation material: according to the on-site layout and adaptation of the construction site, adjust the thickness of the thermal insulation material so that it is lower than the minimum thickness of the old layer at the edge; after aligning the base material, press the thermal insulation material, and knock with a rubber hammer to remove bubbles to ensure a tight fit.

[0019] Preferably, in step S3, the joints are processed: when the gap is ≤10 mm, fill it with primer; when the gap is >10 mm, fill it with insulation material; when the joint drop is ≤5 mm, fill it with putty; when the joint drop is >5 mm, cut and adjust it and fix it with primer.

[0020] Preferably, in step S3, special parts are processed: grooves are cut and glue is applied to protrusions or welds; T-shaped materials, pipes and other parts are spliced on site, and the cut sections are sealed with glass fiber cloth or flame-retardant white cloth; the insulation materials are cut and scored at parts with smaller curvature radius, and the cut depth is adjusted according to the construction location;

[0021] Specifically, step S4 flame retardant layer construction: evenly apply flame retardant white glue (0.8-1.2 kg / m 2 ), paste the flame retardant white cloth; the cloth seams are made by leaving the seams or overlapping. If the seams are left, the width is 5 to 8 mm, and if the overlapping is used, the width is 40 to 50 mm; after the flame retardant white glue is completely cured, apply solvent-free epoxy polyamide transition paint (0.20 to 0.30 kg / m 2 ).

[0022] Specifically, step S5 surface treatment: scrape 3 coats of putty, each coat using 0.8-1.2 kg / m 2 (Total dosage 2.4~3.6kg / m 2 ), polish until smooth after each coat is cured; use solvent-free epoxy topcoat for topcoat, and report to the quality inspection department for acceptance after painting.

[0023] Preferably, the method further includes step S6 of free edge sealing treatment: edge sealing treatment is performed on the exposed portion of the free edge of the thermal insulation material.

[0024] Specifically, the construction environment requirements are: temperature 0~40℃, relative humidity ≤85%; cross-operation is prohibited, tools must be measured and qualified, and material usage must be approved according to the drawings.

[0025] Specifically, the quality inspection nodes are: acceptance of base material primer, acceptance of thermal insulation material pasting, acceptance before putty coating, and acceptance of topcoat completion.

[0026] Preferably, the thermal insulation material is made of the following components in parts by weight: 100-120 parts of polyether polyol, 110-130 parts of diphenylmethane diisocyanate, 8-22 parts of modified filler, 5-9 parts of petroleum ether, 2-6 parts of glycerol, 0.2-1 part of dibutyltin dilaurate, 0.5-1.5 parts of dimethylcyclohexylamine, and 0.8-1.2 parts of pentaerythritol.

[0027] Preferably, the modified filler is prepared by the following method steps:

[0028] (1) dispersing nano-titanium dioxide in an ethanol aqueous solution, ultrasonically treating the solution, adding KH550, stirring the solution for reaction, centrifuging the solution, washing the solution, and drying the solution to obtain amino-treated titanium dioxide;

[0029] Amination of nano-titanium dioxide: KH550 (γ-aminopropyltriethoxysilane) undergoes hydrolysis in an aqueous ethanol solution. The three ethoxy groups react with water to form silanol groups and release ethanol. The hydrolyzed KH550 molecules, through their silanol groups, undergo a condensation reaction with the hydroxyl groups on the surface of the nano-titanium dioxide, forming a Ti-O-Si bond and simultaneously releasing water molecules. After the reaction is complete, the other end of the silane molecule (-CH2CH2CH2NH2) is exposed on the titanium dioxide surface, resulting in an active amino group, forming ammoniated titanium dioxide.

[0030] Preferably, in step (1), nano titanium dioxide

[0031] Preferably, in step (1), the usage ratio of nano-titanium dioxide, ethanol aqueous solution, and KH550 is 10 g: 100-150 mL: 1-3 mL; and the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 85-95: 5-15.

[0032] Preferably, in step (1), the ultrasonic treatment is performed for 10 to 30 minutes; and the stirring reaction conditions are 70 to 80° C. and 4 to 8 hours.

[0033] (2) dispersing the aminated titanium dioxide in THF, then adding triethylamine, slowly adding dropwise the spirocyclic phosphate dichloride solution under stirring and ice bath conditions, warming to room temperature and stirring to react, centrifuging, washing, and drying the product to obtain an intermediate;

[0034] Amination of titanium dioxide reacts with spirocyclic phosphate dichloride: The amino groups on the amination titanium dioxide surface act as nucleophiles, attacking a phosphoryl chloride group (-POCl) in the spirocyclic phosphate dichloride molecule. This then rearranges and releases chloride ions, forming a phosphoamido bond. The HCl produced by the reaction is captured by triethylamine to form triethylamine hydrochloride. The resulting intermediate structure consists of an aminopropyl group connected to the titanium dioxide surface via a Si-O-Ti bond, which is then connected to the spirocyclic phosphate structure via a phosphoamido bond, with the active phosphoryl chloride group retained at the distal end.

[0035] Preferably, in step (2), the usage ratio of amination titanium dioxide, THF, triethylamine, and spirocyclic phosphate dichloride solution is 10 g: 100-120 mL: 3-5 mL: 40-50 mL; and the usage ratio of spirocyclic phosphate dichloride solution to spirocyclic phosphate dichloride is 40-50 mL: 2-4 g.

[0036] Preferably, in step (2), the stirring reaction time is 4 to 8 hours; and the product is washed 3 to 5 times with anhydrous THF and anhydrous ether in sequence.

[0037] (3) Immerse the bamboo fiber in a sodium hydroxide aqueous solution, stir, wash until neutral, dry, then add it to DMF, then add the intermediate and triethylamine, stir and react in a closed container, filter, wash and dry the product to obtain a modified filler.

[0038] Grafting bamboo fiber onto an intermediate: Bamboo fiber is treated with sodium hydroxide, partially dissolving the surface hemicellulose and lignin, exposing more cellulose hydroxyl groups. These active hydroxyl groups then act as nucleophiles, attacking the phosphorus oxychloride groups at the ends of the intermediate molecules, rearranging to release chloride ions and forming phosphate bonds. The HCl produced in the reaction is neutralized by triethylamine. One end of the intermediate molecule is connected to the bamboo fiber via a phosphate bond, while the other end is connected to the amino-treated titanium dioxide via the formed phosphoramide bond.

[0039] Preferably, in step (3), the bamboo fiber has a length of 20 to 30 μm and a diameter of 10 to 15 nm.

[0040] Preferably, in step (3), the usage ratio of bamboo fiber, sodium hydroxide aqueous solution, DMF, intermediate, and triethylamine is 10 g:150-200 mL:100-150 mL:3-5 g:1-3 mL; and the concentration of sodium hydroxide aqueous solution is 10-20 wt %.

[0041] Preferably, in step (3), the stirring reaction conditions are 50-60° C. for 8-14 hours; and the product is washed 3-5 times with anhydrous ethanol and deionized water in sequence.

[0042] Preferably, the thermal insulation material is prepared by the following method steps: stirring and mixing the components except diphenylmethane diisocyanate in proportion for 5 to 15 minutes, then quickly adding diphenylmethane diisocyanate and stirring rapidly for 10 to 30 seconds, introducing the mixture into the mold, closing the mold and placing it in a 40 to 50°C oven for foaming for 1 to 2 hours, and after foaming is completed, the mold is cooled to room temperature with the furnace and demolded to obtain the thermal insulation material.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] 1. The present invention proposes a method for constructing ship hull thermal insulation materials. Through a strict substrate surface treatment process, it ensures a firm bond between the thermal insulation material and the hull substrate, effectively avoiding the risk of peeling during use. The two-way coating technology of the primer and precise dosage control provide a solid bonding foundation for the thermal insulation system. The differentiated treatment solutions for special parts and joints solve the problem of adaptation to complex ship structures, especially the treatment methods for special parts such as T-profiles, pipes, and curved surfaces improve construction efficiency and quality. The multi-layer flame retardant design and strict free-edge sealing treatment not only improve the overall flame retardant performance, but also solve the problem of easy water absorption and aging of traditional thermal insulation materials. Clear environmental condition restrictions and quality inspection node settings ensure that the entire construction process is controllable and traceable, greatly improving the service life and safety and reliability of the thermal insulation system.

[0045] 2. The present invention provides a thermal insulation material, in which polyether polyol and diphenylmethane diisocyanate are used as main reactants to form a tough and stable polyurethane skeleton structure, providing basic thermal insulation performance and structural support. The modified filler introduces a phosphorus-nitrogen synergistic flame retardant system, while improving the mechanical properties and thermal stability of the material. Petroleum ether is used as a physical foaming agent to control the density and porosity of the material and optimize the thermal insulation effect. Glycerol and pentaerythritol are used as cross-linking agents to enhance the network structure and dimensional stability of the material. Dibutyltin dilaurate and dimethylcyclohexylamine are used as a catalytic system to accurately control the reaction rate and pore structure, so that the material has a uniform closed porosity and excellent mechanical properties. The precise ratio of the components and the specific preparation process ensure that the thermal insulation material has the comprehensive characteristics of low thermal conductivity, excellent flame retardancy, suitable density and excellent durability.

[0046] 3. The present invention provides a modified filler. First, nano-titanium dioxide is amino-modified using the silane coupling agent KH550. This not only improves the dispersibility of the nanoparticles but also provides active amino sites for subsequent reactions. The amino groups on the titanium dioxide surface can participate in the foaming reaction of the polyurethane matrix, forming stable chemical bonds with isocyanate groups, enhancing the interfacial compatibility between the filler and the matrix, and improving the pore structure and physical properties of the thermal insulation material. Secondly, a phosphate dichloride with a unique spirocyclic structure is introduced to react with the amino-titanium dioxide, firmly incorporating the phosphorus-based flame retardant element into the structure via a PN bond, forming an intermediate with a synergistic phosphorus-nitrogen flame retardant effect. During high-temperature combustion, the spirocyclic phosphate decomposes to produce oxyphosphoric acid, which promotes the dehydration and carbonization of the filler, forming a dense carbon layer. The nano-titanium dioxide acts as a support site, enhancing the stability of the carbon layer, increasing the residual carbon rate and its oxygen barrier effect, significantly reducing the combustion heat release rate. Finally, alkali-treated bamboo fiber is grafted onto the intermediate to create a "TiO2-PN-bamboo fiber" bridged structure. The hollow, porous structure of the bamboo fiber cell wall disrupts the polyurethane's heat conduction pathways, reducing the material's thermal conductivity. Furthermore, the nano-titanium dioxide coating the bamboo fiber surface forms a thin film, imparting high near-infrared reflectivity and combining both barrier and reflective insulation. This multi-chemically bonded modified filler, through structural design and surface modification, achieves a synergistic improvement in both thermal insulation and flame retardancy, providing critical functional support for thermal insulation materials. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0048] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased from commercial sources or synthesized from commercially purchased raw materials.

[0049] Polyether polyol was purchased from Shandong Jiaying Chemical Technology Co., Ltd., polyether polyol 303;

[0050] Petroleum ether was purchased from Shandong Jiya Technology Co., Ltd., petroleum ether 60-90;

[0051] Nano-titanium dioxide is rutile nano-titanium dioxide, purchased from Yicheng Jingrui Materials Co., Ltd., model number VK-T25.

[0052] A method for preparing a thermal insulation material comprises the following steps:

[0053] (1) Disperse 10 g of nano-titanium dioxide in 100-150 mL of ethanol-water solution (volume ratio of ethanol to deionized water is 85-95:5-15), ultrasonicate for 10-30 min, add 1-3 mL of KH550, stir at 70-80 °C for 4-8 h, centrifuge, wash, and dry the product to obtain amino-titanium dioxide;

[0054] (2) Disperse 10 g of amino titanium dioxide in 100-120 mL of THF, then add 3-5 mL of triethylamine, slowly dropwise add 40-50 mL of spirocyclic phosphate dichloride solution (containing 2-4 g of spirocyclic phosphate dichloride) under stirring and ice bath conditions, warm to room temperature and stir to react for 4-8 hours, centrifuge the product, wash the product with anhydrous THF and anhydrous ether 3-5 times in sequence, and dry to obtain an intermediate;

[0055] (3) 10 g of bamboo fiber was immersed in 150-200 mL of 10-20 wt% sodium hydroxide aqueous solution, stirred, washed until neutral, dried, and then added to 100-150 mL of DMF, followed by adding 3-5 g of the intermediate and 1-3 mL of triethylamine. The mixture was stirred in a sealed container at 50-60° C. for 8-14 h, and the product was filtered, washed with anhydrous ethanol and deionized water for 3-5 times, and dried to obtain a modified filler.

[0056] (4) 100-120 parts of polyether polyol, 8-22 parts of modified filler, 5-9 parts of petroleum ether, 2-6 parts of propylene glycol, 0.2-1 part of dibutyltin dilaurate, 0.5-1.5 parts of dimethylcyclohexylamine, and 0.8-1.2 parts of pentaerythritol are stirred and mixed for 5-15 minutes, and then 110-130 parts of diphenylmethane diisocyanate are quickly added and stirred rapidly for 10-30 seconds. The mixture is introduced into a mold, the mold is closed, and then placed in an oven at 40-50°C for foaming for 1-2 hours. After the foaming is completed, the mold is cooled to room temperature with the furnace and demolded to obtain the thermal insulation material.

[0057] The spirocyclic phosphate dichloride is prepared by the following steps: 42.2g of phosphorus oxychloride, 13.6g of pentaerythritol, and 80mL of chlorobenzene are stirred uniformly, nitrogen is introduced, the temperature is raised to 75°C, and the reaction is carried out for 30 minutes. The temperature is then raised to 115°C, and the reaction is refluxed for 8 hours until hydrogen pentachloride gas is generated. The product is cooled to room temperature, washed with ether, benzene, and dichloromethane in sequence, the solvent is removed by distillation under reduced pressure, and vacuum drying is performed to obtain the spirocyclic phosphate dichloride.

[0058] The present invention will be further described below with reference to specific examples.

[0059] Example 1

[0060] A method for preparing a thermal insulation material comprises the following steps:

[0061] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of ethanol-water solution (the volume ratio of ethanol to deionized water was 95:5), ultrasonically treated for 20 min, 3 mL of KH550 was added, and the mixture was stirred at 80 °C for 4 h. The product was centrifuged, washed, and dried to obtain amino-treated titanium dioxide.

[0062] (2) 10 g of amino-treated titanium dioxide was dispersed in 110 mL of THF, and then 5 mL of triethylamine was added. 45 mL of spirocyclic phosphate dichloride solution (containing 4 g of spirocyclic phosphate dichloride) was slowly added dropwise under stirring and ice bath conditions. The mixture was heated to room temperature and stirred for 8 h. The product was centrifuged and washed four times with anhydrous THF and anhydrous ether, and dried to obtain an intermediate.

[0063] (3) 10 g of bamboo fiber was immersed in 200 mL of 15 wt% sodium hydroxide aqueous solution, stirred, washed until neutral, dried, and then added to 120 mL of DMF. Subsequently, 5 g of the intermediate and 3 mL of triethylamine were added. The mixture was stirred in a sealed container at 60°C for 8 h. The product was filtered, washed four times with anhydrous ethanol and deionized water, and dried to obtain a modified filler.

[0064] (4) 12000 g of polyether polyol, 2200 g of modified filler, 900 g of petroleum ether, 600 g of propylene glycol, 100 g of dibutyltin dilaurate, 150 g of dimethylcyclohexylamine, and 120 g of pentaerythritol were stirred and mixed for 10 minutes, and then 13000 g of diphenylmethane diisocyanate was quickly added and stirred rapidly for 20 seconds. The mixture was introduced into a mold, closed, and placed in a 45°C oven for foaming for 1.5 hours. After the foaming was completed, the mold was cooled to room temperature and demolded to obtain the thermal insulation material.

[0065] Example 2

[0066] A method for preparing a thermal insulation material comprises the following steps:

[0067] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of ethanol-water solution (the volume ratio of ethanol to deionized water was 95:5), ultrasonically treated for 20 min, and 2 mL of KH550 was added. The mixture was stirred at 75 °C for 6 h. The product was centrifuged, washed, and dried to obtain amino-treated titanium dioxide.

[0068] (2) 10 g of amino-treated titanium dioxide was dispersed in 110 mL of THF, and then 4 mL of triethylamine was added. 45 mL of spirocyclic phosphate dichloride solution (containing 3 g of spirocyclic phosphate dichloride) was slowly added dropwise under stirring and ice bath conditions. The mixture was heated to room temperature and stirred for 6 h. The product was centrifuged and washed four times with anhydrous THF and anhydrous ether, and dried to obtain an intermediate.

[0069] (3) 10 g of bamboo fiber was immersed in 200 mL of 15 wt% sodium hydroxide aqueous solution, stirred, washed until neutral, dried, and then added to 120 mL of DMF. Subsequently, 4 g of the intermediate and 2 mL of triethylamine were added. The mixture was stirred in a sealed container at 55°C for 11 h. The product was filtered, washed four times with anhydrous ethanol and deionized water, and dried to obtain a modified filler.

[0070] (4) 11000 g of polyether polyol, 1000 g of modified filler, 700 g of petroleum ether, 400 g of propylene glycol, 60 g of dibutyltin dilaurate, 100 g of dimethylcyclohexylamine, and 100 g of pentaerythritol were stirred and mixed for 10 minutes, and then 12000 g of diphenylmethane diisocyanate was quickly added and stirred rapidly for 20 seconds. The mixture was introduced into a mold, closed, and placed in a 45°C oven for foaming for 1.5 hours. After the foaming was completed, the mold was cooled to room temperature and demolded to obtain the thermal insulation material.

[0071] Example 3

[0072] A method for preparing a thermal insulation material comprises the following steps:

[0073] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of ethanol-water solution (the volume ratio of ethanol to deionized water was 95:5), ultrasonically treated for 20 min, 1 mL of KH550 was added, and the mixture was stirred at 70 °C for 8 h. The product was centrifuged, washed, and dried to obtain amino-treated titanium dioxide.

[0074] (2) 10 g of amino-treated titanium dioxide was dispersed in 110 mL of THF, and then 3 mL of triethylamine was added. 45 mL of spirocyclic phosphate dichloride solution (containing 2 g of spirocyclic phosphate dichloride) was slowly added dropwise under stirring and ice bath conditions. The mixture was heated to room temperature and stirred for 4 h. The product was centrifuged and washed four times with anhydrous THF and anhydrous ether, and dried to obtain an intermediate.

[0075] (3) 10 g of bamboo fiber was immersed in 200 mL of 15 wt% sodium hydroxide aqueous solution, stirred, washed until neutral, dried, and then added to 120 mL of DMF. Subsequently, 3 g of the intermediate and 1 mL of triethylamine were added. The mixture was stirred in a sealed container at 50°C for 14 h. The product was filtered, washed four times with anhydrous ethanol and deionized water, and dried to obtain a modified filler.

[0076] (4) 10,000 g of polyether polyol, 800 g of modified filler, 500 g of petroleum ether, 200 g of propylene glycol, 20 g of dibutyltin dilaurate, 50 g of dimethylcyclohexylamine, and 80 g of pentaerythritol were stirred and mixed for 10 minutes, and then 11,000 g of diphenylmethane diisocyanate was quickly added and stirred rapidly for 20 seconds. The mixture was introduced into a mold, closed, and placed in a 45°C oven for foaming for 1.5 hours. After foaming, the mold was cooled to room temperature with the furnace and demolded to obtain the thermal insulation material.

[0077] Comparative Example 1

[0078] A method for preparing a thermal insulation material comprises the following steps:

[0079] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of ethanol-water solution (the volume ratio of ethanol to deionized water was 95:5), ultrasonically treated for 20 min, and 2 mL of KH550 was added. The mixture was stirred at 75 °C for 6 h. The product was centrifuged, washed, and dried to obtain amino-treated titanium dioxide.

[0080] (2) 10 g of amino-treated titanium dioxide was dispersed in 110 mL of THF, and then 4 mL of triethylamine was added. 45 mL of spirocyclic phosphate dichloride solution (containing 3 g of spirocyclic phosphate dichloride) was slowly added dropwise under stirring and ice bath conditions. The mixture was heated to room temperature and stirred for 6 h. The product was centrifuged and washed four times with anhydrous THF and anhydrous ether, and dried to obtain an intermediate.

[0081] (3) 11000 g of polyether polyol, 1000 g of intermediate, 700 g of petroleum ether, 400 g of propylene glycol, 60 g of dibutyltin dilaurate, 100 g of dimethylcyclohexylamine, and 100 g of pentaerythritol were stirred and mixed for 10 minutes, and then 12000 g of diphenylmethane diisocyanate was quickly added and stirred rapidly for 20 seconds. The mixture was introduced into a mold, closed, and placed in a 45°C oven for foaming for 1.5 hours. After foaming, the mold was cooled to room temperature with the furnace and demolded to obtain the thermal insulation material.

[0082] Comparative Example 2

[0083] A method for preparing a thermal insulation material comprises the following steps:

[0084] (1) 10 g of bamboo fiber was immersed in 200 mL of 15 wt% sodium hydroxide aqueous solution, stirred, washed until neutral, dried, and then added to 120 mL of DMF. 4 mL of triethylamine was then added, and 45 mL of spirocyclic phosphate dichloride solution (containing 3 g of spirocyclic phosphate dichloride) was slowly added dropwise under stirring and ice bath conditions. The mixture was heated to room temperature and stirred for 6 h. The product was centrifuged, washed four times with anhydrous ethanol and deionized water, and dried to obtain modified bamboo fiber.

[0085] (2) 11000 g of polyether polyol, 1000 g of modified bamboo fiber, 700 g of petroleum ether, 400 g of propylene glycol, 60 g of dibutyltin dilaurate, 100 g of dimethylcyclohexylamine, and 100 g of pentaerythritol were stirred and mixed for 10 minutes, and then 12000 g of diphenylmethane diisocyanate was quickly added and stirred rapidly for 20 seconds. The mixture was introduced into a mold, closed, and placed in a 45°C oven for foaming for 1.5 hours. After the foaming was completed, the mold was cooled to room temperature with the furnace and demolded to obtain the thermal insulation material.

[0086] Comparative Example 3

[0087] A method for preparing a thermal insulation material comprises the following steps:

[0088] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of ethanol-water solution (the volume ratio of ethanol to deionized water was 95:5), ultrasonically treated for 20 min, and 2 mL of KH550 was added. The mixture was stirred at 75 °C for 6 h. The product was centrifuged, washed, and dried to obtain amino-treated titanium dioxide.

[0089] (2) 10 g of bamboo fiber was immersed in 200 mL of a 15 wt% sodium hydroxide aqueous solution, stirred, washed until neutral, and dried. The mixture was then added to 120 mL of DMF. 3 g of amino titanium dioxide and 1 g of spirocyclic phosphate dichloride were then added. The mixture was stirred and mixed at room temperature for 2 h. The product was filtered and dried to obtain a mixed filler.

[0090] (3) 11000 g of polyether polyol, 1000 g of mixed filler, 700 g of petroleum ether, 400 g of propylene glycol, 60 g of dibutyltin dilaurate, 100 g of dimethylcyclohexylamine, and 100 g of pentaerythritol were stirred and mixed for 10 minutes, and then 12000 g of diphenylmethane diisocyanate was quickly added and stirred rapidly for 20 seconds. The mixture was introduced into a mold, closed, and placed in a 45°C oven for foaming for 1.5 hours. After foaming, the mold was cooled to room temperature with the furnace and demolded to obtain the thermal insulation material.

[0091] The thermal insulation materials of Examples 1-3 and Comparative Examples 1-3 were prepared into 300 mm × 300 mm × 30 mm specimens for product performance testing. Tensile strength and elongation at break were tested according to ISO 1798-2008, "Elastic porous polymer materials—Determination of tensile strength and elongation at break." Thermal conductivity was tested according to GB / T 10295-2008, "Thermal insulation materials—Determination of steady-state thermal resistance and related properties—Heat flow meter method." Oxygen permeability was tested according to GB / T 1038.1-2022, "Plastics—Film and sheeting—Test method for gas permeability—Part 1: Differential pressure method." Fire rating was tested according to GB / T 2408-2021, "Plastics—Determination of burning behavior—Horizontal and vertical methods." Specific data are shown in Table 1.

[0092] Table 1 Thermal insulation material performance test results

[0093]

[0094] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for constructing a thermal insulation material for a ship hull, characterized in that: The steps include: S1. Substrate surface treatment: Clean and roughen the substrate surface; S2. Primer coating: Apply adhesive evenly on the contact surface between the substrate and the thermal insulation material; S3.Insulation material installation: Press the insulation material onto the substrate surface and treat the seams; S4. Flame retardant coating: Lay flame retardant fabric and transition coating on the surface of the insulation material in sequence; S5. Surface treatment: Apply multiple layers of putty and topcoat.

2. The construction method according to claim 1, characterized in that: The thermal insulation material is made of the following components in parts by weight: 100-120 parts of polyether polyol, 110-130 parts of diphenylmethane diisocyanate, 8-22 parts of modified filler, 5-9 parts of petroleum ether, 2-6 parts of glycerol, 0.2-1 part of dibutyltin dilaurate, 0.5-1.5 parts of dimethylcyclohexylamine, and 0.8-1.2 parts of pentaerythritol.

3. The construction method according to claim 2, characterized in that: The modified filler is prepared by the following steps: (1) dispersing nano-titanium dioxide in an ethanol aqueous solution, ultrasonically treating the solution, adding KH550, stirring the solution for reaction, centrifuging the solution, washing the solution, and drying the solution to obtain amino-treated titanium dioxide; (2) dispersing the aminated titanium dioxide in THF, then adding triethylamine, slowly adding dropwise the spirocyclic phosphate dichloride solution under stirring and ice bath conditions, warming to room temperature and stirring to react, centrifuging, washing, and drying the product to obtain an intermediate; (3) Immerse the bamboo fiber in a sodium hydroxide aqueous solution, stir, wash until neutral, dry, then add it to DMF, then add the intermediate and triethylamine, stir and react in a closed container, filter, wash and dry the product to obtain a modified filler.

4. The construction method according to claim 3, characterized in that: In step (1), the dosage ratio of nano-titanium dioxide, ethanol aqueous solution and KH550 is 10g:100-150mL:1-3mL; the volume ratio of ethanol and deionized water in the ethanol aqueous solution is 85-95:5-15.

5. The construction method according to claim 3, characterized in that: In step (1), the ultrasonic treatment is performed for 10 to 30 minutes; and the stirring reaction condition is 70 to 80° C. and the stirring reaction is performed for 4 to 8 hours.

6. The construction method according to claim 3, characterized in that: In step (2), the usage ratio of amination titanium dioxide, THF, triethylamine, and spirocyclic phosphate dichloride solution is 10 g: 100-120 mL: 3-5 mL: 40-50 mL; and the usage ratio of spirocyclic phosphate dichloride solution to spirocyclic phosphate dichloride is 40-50 mL: 2-4 g.

7. The construction method according to claim 3, characterized in that: In step (2), the stirring reaction time is 4 to 8 hours; the product is washed 3 to 5 times with anhydrous THF and anhydrous ether in sequence.

8. The construction method according to claim 3, characterized in that: In step (3), the usage ratio of bamboo fiber, sodium hydroxide aqueous solution, DMF, intermediate, and triethylamine is 10 g:150-200 mL:100-150 mL:3-5 g:1-3 mL; and the concentration of sodium hydroxide aqueous solution is 10-20 wt %.

9. The construction method according to claim 3, characterized in that: In step (3), the stirring reaction conditions are 50-60° C. and 8-14 h; the product is washed 3-5 times with anhydrous ethanol and deionized water in sequence.

10. The construction method according to claim 2, characterized in that: The thermal insulation material is prepared by the following method steps: stirring and mixing the components except diphenylmethane diisocyanate in proportion for 5 to 15 minutes, then quickly adding diphenylmethane diisocyanate and stirring rapidly for 10 to 30 seconds, introducing the mixture into a mold, closing the mold, and placing it in a 40 to 50° C. oven for foaming for 1 to 2 hours. After the foaming is completed, the mold is cooled in the oven to room temperature and demoulded to obtain the thermal insulation material.

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