A method for the application of thermal insulation to a ship hull

Abstract

The application discloses a heat 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, heat insulation material installation, flame-retardant layer construction, and surface treatment.The heat insulation material is made of the following components in parts by weight: polyether polyol 100-120 parts, diphenyl methane diisocyanate 110-130 parts, modified filler 8-22 parts, petroleum ether 5-9 parts, glycerol 2-6 parts, dibutyl tin dilaurate 0.2-1 part, dimethylcyclohexylamine 0.5-1.5 parts, and pentaerythritol 0.8-1.2 parts.The heat insulation material integrates excellent heat insulation performance and outstanding flame-retardant characteristics, can exhibit excellent size stability and durability in harsh environments such as high temperature, high humidity and vibration of the ship, and provides a safe and reliable comprehensive heat insulation solution for the ship.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ship construction, in particular to a heat insulation material construction method for ship hulls. BACKGROUND

[0002] Ship insulation materials are a key component of ship construction and maintenance, directly affecting the safety, comfort and energy efficiency of ships. With the continuous improvement of the International Maritime Organization (IMO) standards for ship fire safety and the increasing strictness of shipowners' requirements for energy saving and emission reduction, the research and application of high-performance insulation materials and their supporting construction technology have become particularly important.

[0003] Traditional ship insulation materials mainly include mineral wool, glass wool, polyurethane foam, etc. These materials are usually constructed by mechanical fixation, adhesion or spraying, etc. Among them, mineral wool and glass wool are prone to produce dust hazards to workers' health during construction, and have the problems of strong water absorption and easy aging; while conventional polyurethane foam has good thermal insulation performance, but its flame retardancy is insufficient, and the construction process is complex, which is prone to problems such as poor adhesion, improper joint treatment, etc. in the special environment of ship high temperature, high humidity, vibration, etc., leading to peeling and falling off of the insulation layer, reducing the service life and increasing the safety hazards.

[0004] In the existing insulation material construction method, the problems of non-standard surface treatment of base material, improper joint treatment, poor adaptability of special parts, etc. are more prominent. Especially in the construction of complex ship structures (such as T-shaped material, pipeline crossing, curved surface, etc.), the imperfect construction method often leads to local failure of the thermal insulation effect. In addition, the existing construction method is insufficient in edge sealing treatment of free edges of materials, making the insulation material prone to deformation due to moisture, and lacks systematic quality control nodes and environmental condition restrictions, making it difficult to ensure the construction quality.

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

[0006] In terms of insulation materials, traditional materials often single-mindedly pursue thermal insulation performance or flame retardant performance, making it difficult to meet both requirements. Especially in the ship environment, the flame retardancy, durability and adaptability of the insulation material are extremely high, and the performance of the existing materials often cannot meet the actual application requirements of ships. In addition, the uneven dispersion and poor compatibility of the fillers inside the insulation material also lead to unstable material performance and short service life.

[0007] Therefore, it is of great significance to develop a high-performance ship heat insulation material and a systematic and standardized construction method to solve the performance defects of the material and the construction process defects in the prior art, and to improve the safety of the ship, prolong the service life, and reduce the maintenance cost. SUMMARY

[0008] In order to solve the problems in the prior art, the present application provides a heat insulation material construction method for a ship body, which integrates excellent heat insulation performance and excellent flame retardant properties, effectively solves the problems of easy aging and insufficient flame retardancy of traditional heat insulation materials, and can exhibit excellent dimensional stability and durability in harsh environments such as high temperature, high humidity and vibration of the ship, thereby providing a safe and reliable comprehensive heat insulation solution for the ship.

[0009] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0010] A heat insulation material construction method for a ship body, comprising the following steps:

[0011] S1. Surface treatment of base material: cleaning and roughening the surface of the base material;

[0012] S2. Primer coating: uniformly coating adhesive on the contact surface of the base material and the heat insulation material;

[0013] S3. Heat insulation material installation: pressing the heat insulation material to the surface of the base material and treating the joint;

[0014] S4. Flame retardant layer construction: sequentially laying flame retardant fabric and transition coating on the surface of the heat insulation material;

[0015] S5. Surface treatment: performing multi-layer putty scraping and topcoat painting.

[0016] Specifically, step S1, surface treatment of base material: ensure that the surface of the base material has been primed and accepted by the quality inspection department; use cleaning tools to remove water, oil stains, paint skin and impurities on the surface of the base material to ensure that the surface is dry; roughen the surface of the primer to increase roughness, and wipe the surface residues with a clean cloth.

[0017] Specifically, step S2, primer coating: stir the primer to a uniform state, the construction environment temperature is 5-40 DEG C, and the relative humidity is less than or equal to 85%; uniformly coat the primer on the contact surface of the base material and the heat insulation material in both directions, the coating amount is 2.5-3.5 kg / m 2 , and ensure that there is no missed coating; if the base material surface is frosted or the temperature is lower than 0 DEG C, the construction needs to be suspended.

[0018] Specifically, in step S3, the thermal insulation material is installed: according to the site layout adaptation of the construction site, the thickness of the thermal insulation material is adjusted to be lower than the minimum thickness of the edge old layer; after aligning the base material, the thermal insulation material is pressed and closed, and the rubber hammer is knocked to exhaust bubbles to ensure close fitting.

[0019] Preferably, in step S3, the joint treatment: when the gap is ≤10 mm, the joint is filled with primer; when the gap is >10 mm, the joint is filled with thermal insulation material; when the joint gap is ≤5 mm, the joint is filled with putty; when the joint gap is >5 mm, the joint is cut and adjusted and fixed with primer.

[0020] Preferably, in step S3, the special part treatment: a groove is cut at the protrusion or weld and glued; the T-shaped material, pipeline and other parts are spliced on site, and the cut section is sealed with glass fiber cloth or fire-retardant white cloth; the thermal insulation material is cut and processed at the part with small curvature radius, and the depth of the cut is adjusted according to the construction site;

[0021] Specifically, in step S4, the fire-retardant layer is constructed: the fire-retardant white glue (0.8-1.2 kg / m 2 ) is uniformly brushed on the surface of the thermal insulation material, and the fire-retardant white cloth is pasted; the cloth joint is left with a gap or overlapped, if the left gap construction is adopted, the width is 5-8 mm, and if the overlapping construction is adopted, the width is 40-50 mm; after the fire-retardant white glue is completely cured, the solvent-free epoxy polyamide transition paint (0.20-0.30 kg / m 2 ) is applied.

[0022] Specifically, in step S5, the surface treatment: 3 coats of putty are brushed, each coat uses 0.8-1.2 kg / m 2 (total amount 2.4-3.6 kg / m 2 ), and each coat is polished to be flat after curing; the topcoat is selected from the solvent-free epoxy topcoat, and after the topcoat is applied, it is submitted to the quality inspection department for acceptance.

[0023] Preferably, it further includes step S6, the free edge sealing treatment: the free edge exposed part of the thermal insulation material is sealed.

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

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

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

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

[0028] (1) dispersing nano-titania into an ethanol aqueous solution, ultrasonic treatment, adding KH550, stirring reaction, centrifuging, washing, drying the product to obtain aminated titania;

[0029] Amination of nano-titania: KH550 (γ-aminopropyltriethoxysilane) first undergoes a hydrolysis reaction in an ethanol aqueous solution, three ethoxyl groups react with water to form silanol groups and release ethanol. The hydrolyzed KH550 molecules react with the hydroxyl groups on the surface of nano-titania through their silanol groups to form Ti-O-Si bonds and release water molecules. After the reaction is completed, the other end of the silane molecule (-CH2CH2CH2NH2) is exposed on the surface of the titania, so that it obtains active amino groups and forms aminated titania.

[0030] Preferably, in step (1), the nano-titania

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

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

[0033] (2) dispersing the aminated titania into THF, then adding triethylamine, slowly adding a spirocyclic phosphate diacyl chloride solution under stirring and ice bath conditions, stirring at room temperature, centrifuging, washing, and drying the product to obtain an intermediate;

[0034] Reaction of aminated titania with spirocyclic phosphate diacyl chloride: the amino groups on the surface of the aminated titania act as nucleophiles to attack one of the phosphoryl chloride groups (-POCl) in the spirocyclic phosphate diacyl chloride molecule, followed by rearrangement and release of chloride ions to form a phosphoramidate bond. The HCl produced in the reaction is captured by triethylamine to form a triethylamine hydrochloride salt. The final intermediate structure is that the amino propyl group is connected to the surface of the titania through a Si-O-Ti bond, and the spirocyclic phosphate structure is connected through a phosphoramidate bond, and an active phosphoryl chloride group is retained at the distal end.

[0035] Preferably, in step (2), the amount ratio of aminated titania, THF, triethylamine, and spirocyclic phosphate diacyl chloride solution is 10 g: 100-120 mL: 3-5 mL: 40-50 mL; the amount ratio of the spirocyclic phosphate diacyl chloride solution to spirocyclic phosphate diacyl chloride is 40-50 mL: 2-4 g.

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

[0037] (3) The bamboo fiber is immersed in sodium hydroxide aqueous solution, stirred and treated, washed until neutral, dried, then added into DMF, followed by adding intermediate and triethylamine, closed stirring reaction, the product is filtered, washed and dried to obtain the modified filler.

[0038] The bamboo fiber is treated by sodium hydroxide, and part of hemicellulose and lignin on the surface is dissolved, exposing more cellulose hydroxyl groups, which then act as nucleophiles to attack the terminal phosphoryl chloride group of the intermediate molecule, releasing chloride ions, forming a phosphate ester bond, and the HCl produced in the reaction is neutralized by triethylamine. One end of the intermediate molecule is connected to the bamboo fiber through the phosphate ester bond, and the other end is connected to the aminated titanium dioxide through the formed phosphoramide bond.

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

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

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

[0042] Preferably, the thermal insulation material is prepared by the following method steps: the components except for diphenyl methane diisocyanate are stirred and mixed in proportion for 5-15min, then diphenyl methane diisocyanate is quickly added, and the mixture is quickly stirred for 10-30s, then the mixture is introduced into a mold for molding, and then placed in an oven at 40-50℃ for foaming for 1-2h, after foaming is completed, the mold is cooled to room temperature with the oven, and then demolded to obtain the thermal insulation material.

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

[0044] 1. The application provides a ship hull thermal insulation material construction method, which ensures firm adhesion between the thermal insulation material and the hull base material through strict base material surface treatment process, effectively avoids peeling risk in use process. The bidirectional coating technology of primer and precise dosage control provide a solid adhesion foundation for the thermal insulation system. The differentiated treatment scheme for special parts and joints solves the adaptation problem of complex ship structure, especially the treatment method for special parts such as T-shaped material, pipeline and curved surface improves the 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 problems of easy water absorption and aging of traditional thermal insulation materials. The clear environmental condition limitation and quality inspection node setting ensure the controllability and traceability of the whole construction process, greatly improve the service life and safety reliability of the thermal insulation system.

[0045] 2. The application provides a kind of thermal insulation material, polyether polyol and diphenyl methane diisocyanate as main reactants, form tough and stable polyurethane skeleton structure, provide basic thermal insulation performance and structural support. Modified filler introduces phosphorus-nitrogen synergistic flame-retardant system, while improving the mechanical properties and thermal stability of the material. Petroleum ether as a physical foaming agent, control material density and porosity, optimize the thermal insulation effect. Glycerol and pentaerythritol as crosslinking agent, enhance the network structure and dimensional stability of the material. Dibutyltin dilaurate and dimethylcyclohexylamine as catalytic system, accurate control of reaction rate and cell structure, make the material have uniform closed cell rate and excellent mechanical properties. The accurate proportioning of each component and 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 application provides a modified filler, first, the nano titanium dioxide is modified by amino through a silane coupling agent KH550, which not only improves the dispersibility of the nanoparticles, but also provides active amino sites for subsequent reactions. The amino on the surface of the titanium dioxide can participate in the foaming reaction of the polyurethane matrix, form stable chemical bonds with isocyanate groups, improve the interfacial compatibility of the filler and the matrix, and improve the cell structure and physical properties of the thermal insulation material. Secondly, the phosphonate dichloride with a special spiro ring structure is introduced to react with the aminated titanium dioxide, and the phosphorus-based flame-retardant elements are firmly introduced into the structure through P-N bonds to form an intermediate with phosphorus-nitrogen synergistic flame-retardant effect. The spirophosphonate decomposes to generate oxygen-containing phosphoric acid during high-temperature combustion, promotes the dehydration and carbonization of the filler to form a dense carbon layer, and the nano titanium dioxide serves as a support site to enhance the stability of the carbon layer, improve the carbon residue rate and oxygen barrier effect, and significantly reduce the heat release rate during combustion. Finally, the alkali-treated bamboo fiber is grafted with the intermediate to construct a bridging structure of "TiO2-P-N-bamboo fiber". The hollow porous structure of the bamboo fiber cell wall can destroy the heat conduction path of the polyurethane, reducing the thermal conductivity of the material; at the same time, the nano titanium dioxide is coated on the surface of the bamboo fiber to form a film, giving the material high near-infrared reflectivity, integrating the barrier insulation and reflective insulation functions in one. This modified filler with multiple chemical bonds realizes the synergistic improvement of thermal insulation performance and flame-retardant effect through structure design and surface modification, providing key functional support for thermal insulation materials. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with examples. Of course, the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0048] Unless otherwise specified, the chemical reagents and materials in the present application are purchased through market channels or synthesized from raw materials purchased through market channels.

[0049] The polyether polyol is purchased from Shandong Jiaying Chemical Technology Co., Ltd., and the polyether polyol 303 is purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0050] The petroleum ether is purchased from Shandong Jiaying Chemical Technology Co., Ltd., and the petroleum ether 60-90 is purchased from Shandong Jiaying Chemical Technology Co., Ltd.

[0051] The nano titanium dioxide is rutile type nano titanium dioxide, purchased from Yicheng Jingrui Material Co., Ltd., and the model is VK-T25.

[0052] A preparation method of a thermal insulation material, comprising the following steps:

[0053] (1) dispersing 10 g of nano-titanium dioxide into 100-150 mL of an ethanol aqueous solution (volume ratio of ethanol to deionized water is 85-95:5-15), ultrasonic treatment for 10-30 min, adding 1-3 mL of KH550, stirring and reacting at 70-80℃ for 4-8 h, centrifuging, washing and drying the product to obtain aminated titanium dioxide;

[0054] (2) dispersing 10 g of aminated titanium dioxide into 100-120 mL of THF, then adding 3-5 mL of triethylamine, slowly dropping 40-50 mL of a spirocyclic phosphate diacyl chloride solution (containing 2-4 g of spirocyclic phosphate diacyl chloride) under stirring and ice bath condition, stirring and reacting at room temperature for 4-8 h, centrifuging, washing the product with anhydrous THF and anhydrous diethyl ether for 3-5 times in sequence, and drying to obtain an intermediate;

[0055] (3) immersing 10 g of bamboo fiber into 150-200 mL of a 10-20 wt% sodium hydroxide aqueous solution, stirring and treating, washing until neutral, drying, then adding into 100-150 mL of DMF, then adding 3-5 g of the intermediate and 1-3 mL of triethylamine, stirring and reacting at 50-60℃ in a closed state for 8-14 h, filtering the product, washing with anhydrous ethanol and deionized water for 3-5 times in sequence, and drying to obtain a modified filler;

[0056] (4) stirring and mixing 100-120 parts of polyether polyol, 8-22 parts of the 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, 0.8-1.2 parts of pentaerythritol for 5-15 min, then rapidly adding 110-130 parts of diphenylmethane diisocyanate, rapidly stirring for 10-30 s, introducing the mixture into a mold, and placing in a 40-50℃ oven for foaming for 1-2 h, after foaming, the mold is cooled to room temperature with the oven and demolded to obtain the heat insulation material.

[0057] The spirocyclic phosphate diacyl chloride is prepared by the following method steps: stirring 42.2 g of phosphorus oxychloride, 13.6 g of pentaerythritol and 80 mL of chlorobenzene uniformly, introducing nitrogen, increasing the temperature to 75℃, reacting for 30 min, increasing the temperature to 115℃, refluxing for 8 h until hydrogen chloride gas is generated, cooling the product to room temperature, washing with diethyl ether, benzene and dichloromethane in sequence, removing the solvent by reduced pressure distillation, and vacuum drying to obtain the spirocyclic phosphate diacyl chloride.

[0058] The application will be further described below through specific examples.

[0059] Example 1

[0060] A preparation method of a heat insulation material, comprising the following steps:

[0061] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of an ethanol aqueous solution (volume ratio of ethanol to deionized water was 95:5), ultrasonic treatment was performed for 20 min, 3 mL of KH550 was added, stirring reaction was performed at 80°C for 4 h, the product was centrifuged, washed, and dried to obtain aminated titanium dioxide;

[0062] (2) 10 g of aminated titanium dioxide was dispersed in 110 mL of THF, then 5 mL of triethylamine was added, 45 mL of a spirocyclic phosphate diacyl chloride solution (containing 4 g of spirocyclic phosphate diacyl chloride) was slowly added dropwise under stirring and ice bath conditions, stirring reaction was performed at room temperature for 8 h, the product was centrifuged, the product was washed with anhydrous THF and anhydrous diethyl ether four times in sequence, and dried to obtain an intermediate;

[0063] (3) 10 g of bamboo fibers were immersed in 200 mL of a 15 wt% sodium hydroxide aqueous solution, stirring treatment was performed, washing was performed until neutral, and drying was performed, then the bamboo fibers were added to 120 mL of DMF, then 5 g of the intermediate and 3 mL of triethylamine were added, stirring reaction was performed at 60°C for 8 h in a closed state, the product was filtered, washed with anhydrous ethanol and deionized water four times in sequence, and dried to obtain a modified filler;

[0064] (4) 12000 g of a polyether polyol, 2200 g of the modified filler, 900 g of petroleum ether, 600 g of glycerol, 100 g of dibutyltin dilaurate, 150 g of dimethylcyclohexylamine, and 120 g of pentaerythritol were stirred and mixed for 10 min, then 13000 g of diphenylmethane diisocyanate was quickly added, rapid stirring was performed for 20 s, the mixture was introduced into a mold and combined, and then placed in a 45°C oven to foam for 1.5 h, after the foaming was completed, the mold was cooled to room temperature with the oven and demolded, to obtain the thermal insulation material.

[0065] Example 2

[0066] A preparation method of a thermal insulation material, comprising the following steps:

[0067] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of an ethanol aqueous solution (volume ratio of ethanol to deionized water was 95:5), ultrasonic treatment was performed for 20 min, 3 mL of KH550 was added, stirring reaction was performed at 80°C for 4 h, the product was centrifuged, washed, and dried to obtain aminated titanium dioxide;

[0068] (2) 10 g of aminated titanium dioxide was dispersed in 110 mL of THF, then 5 mL of triethylamine was added, 45 mL of a spirocyclic phosphate diacyl chloride solution (containing 4 g of spirocyclic phosphate diacyl chloride) was slowly added dropwise under stirring and ice bath conditions, stirring reaction was performed at room temperature for 8 h, the product was centrifuged, the product was washed with anhydrous THF and anhydrous diethyl ether four times in sequence, and dried to obtain an intermediate;

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

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

[0071] Example 3

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

[0073] (1) 10 g of nanometer titanium dioxide was dispersed in 150 mL of an ethanol aqueous solution (volume ratio of ethanol to deionized water was 95:5), and ultrasonic treatment was performed for 20 min. 1 mL of KH550 was added, and stirring reaction was performed at 70°C for 8 h. The product was centrifuged, washed, and dried to obtain aminated titanium dioxide;

[0074] (2) 10 g of aminated titanium dioxide was dispersed in 110 mL of THF, and then 3 mL of triethylamine was added. 45 mL of a spirophosphate diacyl chloride solution (containing 2 g of spirophosphate diacyl chloride) was slowly added dropwise under stirring and ice bath conditions. The temperature was increased to room temperature, and stirring reaction was performed for 4 h. The product was centrifuged, and the product was washed with anhydrous THF and anhydrous diethyl ether four times in turn, and dried to obtain the intermediate;

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

[0076] (4) Polyether polyol 10000 g, modified filler 800 g, petroleum ether 500 g, glycerol 200 g, dibutyltin dilaurate 20 g, dimethylcyclohexylamine 50 g, pentaerythritol 80 g were stirred and mixed for 10 min, then diphenylmethane diisocyanate 11000 g was quickly added, and the mixture was quickly stirred for 20 s. The mixture was introduced into a mold and molded, and then placed in a 45°C oven for foaming for 1.5 h. After the foaming was completed, the mold was cooled to room temperature with the oven and demolded to obtain the thermal insulation material.

[0077] Comparative Example 1

[0078] A preparation method of a thermal insulation material, comprising the following steps:

[0079] (1) 10 g of nano-titanium dioxide was dispersed in 150 mL of an ethanol aqueous solution (the volume ratio of ethanol to deionized water was 95:5), and ultrasonic treatment was performed for 20 min. Then, 2 mL of KH550 was added, and stirring reaction was performed at 75°C for 6 h. The product was centrifuged, washed, and dried to obtain aminated titanium dioxide;

[0080] (2) 10 g of the aminated titanium dioxide was dispersed in 110 mL of THF, and then 4 mL of triethylamine was added. Under the conditions of stirring and ice bath, 45 mL of a spirophosphate diacyl chloride solution (containing 3 g of spirophosphate diacyl chloride) was slowly added dropwise. The temperature was increased to room temperature, and stirring reaction was performed for 6 h. The product was centrifuged, and the product was washed with anhydrous THF and anhydrous diethyl ether four times in sequence, and dried to obtain an intermediate;

[0081] (3) Polyether polyol 11000 g, intermediate 1000 g, petroleum ether 700 g, glycerol 400 g, dibutyltin dilaurate 60 g, dimethylcyclohexylamine 100 g, pentaerythritol 100 g were stirred and mixed for 10 min, then diphenylmethane diisocyanate 12000 g was quickly added, and the mixture was quickly stirred for 20 s. The mixture was introduced into a mold and molded, and then placed in a 45°C oven for foaming for 1.5 h. After the foaming was completed, the mold was cooled to room temperature with the oven and demolded to obtain the thermal insulation material.

[0082] Comparative Example 2

[0083] A preparation method of a thermal insulation material, comprising the following steps:

[0084] (1) 10 g of bamboo fiber was immersed in 200 mL of a 15wt% sodium hydroxide aqueous solution, and stirring treatment was performed. Washing was performed until neutral, and then drying was performed. Then, the bamboo fiber was added to 120 mL of DMF, and then 4 mL of triethylamine was added. Under the conditions of stirring and ice bath, 45 mL of a spirophosphate diacyl chloride solution (containing 3 g of spirophosphate diacyl chloride) was slowly added dropwise. The temperature was increased to room temperature, and stirring reaction was performed for 6 h. The product was centrifuged, and washed with anhydrous ethanol and deionized water four times in sequence, and dried to obtain modified bamboo fiber;

[0085] (2) Stir and mix 11000 g of polyether polyol, 1000 g of modified bamboo fiber, 700 g of petroleum ether, 400 g of glycerol, 60 g of dibutyltin dilaurate, 100 g of dimethylcyclohexylamine, and 100 g of pentaerythritol for 10 min, then quickly add 12000 g of diphenylmethane diisocyanate, stir quickly for 20 s, introduce the mixture into a mold, and then place it in a 45℃ oven for 1.5 h to foam, after the foaming is completed, the mold is cooled to room temperature with the oven and demolded, to obtain the thermal insulation material.

[0086] Comparative Example 3

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

[0088] (1) Disperse 10 g of nano-titanium dioxide into 150 mL of an ethanol aqueous solution (the volume ratio of ethanol to deionized water is 95:5), ultrasonic treatment for 20 min, add 2 mL of KH550, stir at 75℃ for 6 h, centrifuge, wash, and dry the product to obtain aminated titanium dioxide;

[0089] (2) Soak 10 g of bamboo fiber in 200 mL of a 15wt% sodium hydroxide aqueous solution, stir and treat, wash to neutral, and dry, then add to 120 mL of DMF, then add 3 g of aminated titanium dioxide and 1 g of spirocyclic phosphate diacyl chloride, stir and mix at room temperature for 2 h, filter and dry the product to obtain a mixed filler;

[0090] (3) Stir and mix 11000 g of polyether polyol, 1000 g of the mixed filler, 700 g of petroleum ether, 400 g of glycerol, 60 g of dibutyltin dilaurate, 100 g of dimethylcyclohexylamine, and 100 g of pentaerythritol for 10 min, then quickly add 12000 g of diphenylmethane diisocyanate, stir quickly for 20 s, introduce the mixture into a mold, and then place it in a 45℃ oven for 1.5 h to foam, after the foaming is completed, the mold is cooled to room temperature with the oven and demolded, to obtain the thermal insulation material.

[0091] Prepare samples of 300 mm x 300 mm x 30 mm of the thermal insulation materials of Examples 1-3 and Comparative Examples 1-3 to detect the product performance, test the tensile strength and elongation at break according to ISO 1798-2008 “Elastomeric cellular thermoplastic materials— Determination of tensile strength and elongation at break”, test the thermal conductivity according to GB / T 10295-2008 “Determination of thermal resistance and related properties of thermal insulation materials— Hot-wire method”, test the oxygen transmission coefficient according to GB / T 1038.1-2022 “Plastics— Determination of gas transmission properties— Part 1: Differential pressure method”, and test the fire resistance grade according to GB / T 2408-2021 “Determination of the flammability of plastics— Horizontal and vertical method”. The specific data are shown in Table 1.

[0092] Table 1 Thermal insulation material performance test results

[0093]

[0094] The above merely provides the preferred embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical solution and the inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, should be covered within the protection scope of the present application.

Claims

1. A method for the application of thermal insulation material to a ship's hull, characterised in that, It comprises the following steps: S1. substrate surface treatment: cleaning and roughening treatment on the surface of the substrate; S2. primer coating: uniformly coating adhesive on the contact surface of the substrate and the thermal insulation material; S3. thermal insulation material installation: pressing the thermal insulation material to the surface of the substrate and treating the joint; S4. fire-retardant layer construction: laying the fire-retardant fabric and the transition coating on the surface of the thermal insulation material in turn; S5. surface treatment: carrying out multi-layer putty scraping and topcoat painting; The thermal insulation material is made of the following components in parts by weight: polyether polyol 100-120 parts, diphenyl methane diisocyanate 110-130 parts, modified filler 8-22 parts, petroleum ether 5-9 parts, glycerol 2-6 parts, dibutyltin dilaurate 0.2-1 part, dimethylcyclohexylamine 0.5-1.5 parts, and pentaerythritol 0.8-1.2 parts; The modified filler is prepared by the following steps: (1) dispersing nano titanium dioxide into an ethanol aqueous solution, ultrasonic treatment, adding KH550, stirring and reacting, centrifuging, washing and drying the product to obtain aminated titanium dioxide; (2) dispersing the aminated titanium dioxide into THF, then adding triethylamine, slowly dropping a spirocyclic phosphate diacyl chloride solution under stirring and ice bath conditions, stirring and reacting at room temperature, centrifuging, washing and drying the product to obtain an intermediate; (3) immersing bamboo fibers into a sodium hydroxide aqueous solution, stirring and treating, washing to neutral, drying, then adding into DMF, subsequently adding the intermediate and triethylamine, stirring and reacting in a sealed state, filtering, washing and drying the product to obtain the modified filler.

2. The construction method according to claim 1, characterized in that, In step (1), the amount ratio of nano titanium dioxide, the 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.

3. The construction method according to claim 2, characterized in that, In step (1), the ultrasonic treatment is 10-30min; the stirring and reaction conditions are 70-80℃ stirring and reaction for 4-8h.

4. The construction method according to claim 1, characterized in that, In step (2), the amount ratio of aminated titanium dioxide, THF, triethylamine, and spirocyclic phosphate diacyl chloride solution is 10g: 100-120mL: 3-5mL: 40-50mL; the amount ratio of the spirocyclic phosphate diacyl chloride solution to spirocyclic phosphate diacyl chloride is 40-50mL: 2-4g.

5. The construction method according to claim 1, characterized in that, In step (2), the stirring and reaction time is 4-8h; the product is washed with anhydrous THF and anhydrous diethyl ether for 3-5 times in turn.

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

7. The construction method according to claim 1, characterized in that, In step (3), the stirring and reaction conditions are 50-60℃ stirring and reaction for 8-14h; the product is washed with anhydrous ethanol and deionized water for 3-5 times in turn.

8. The construction method according to claim 1, characterized in that, The heat insulation material is prepared by the following method steps: mixing the components except diphenyl methane diisocyanate in proportion for 5-15 min, then quickly adding diphenyl methane diisocyanate, quickly stirring for 10-30 s, introducing the mixture into a mold to combine, and then placing the mold in an oven at 40-50 DEG C for foaming for 1-2 h; after foaming is completed, the mold is cooled to room temperature with the oven and demolded to obtain the heat insulation material.

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