Environment-friendly thermal insulation polyurethane foam and preparation method thereof

Abstract

The present application relates to the technical field of polyurethane materials, in particular to an environment-friendly thermal insulation polyurethane foam material and a preparation method thereof.The environment-friendly thermal insulation polyurethane foam material comprises component A and component B;the mass ratio of the component A to the component B is 1:1;the component A comprises the following raw materials in parts by weight: castor oil composite polyol 40-70 parts, polyether polyol 20-40 parts, functional dihydric alcohol 5-10 parts, foam stabilizer 1-3 parts, foaming agent 2-5 parts, catalyst 0.5-2 parts, and pore-forming agent 1-3 parts;the component B is isocyanate;the castor oil composite polyol is composed of castor oil and castor oil derivative polyol in a mass ratio of 2: (1-1.5).The environment-friendly thermal insulation polyurethane foam material realizes an optimized balance between mechanical strength and flame retardant performance, not only has high structural support strength, but also effectively improves the fire safety grade.

Description

Technical Field

[0001] This invention relates to the field of polyurethane materials technology, specifically to an environmentally friendly thermal insulation polyurethane foam material and its preparation method. Background Technology

[0002] Polyurethane flexible foam is made from polyols and isocyanates through the foaming action of a foaming agent. It features a soft texture, good resilience, low compression set, and an ideal deformation curve, and is widely used in construction, automotive, furniture, and packaging industries. Among these applications, building insulation has become one of its core applications.

[0003] However, the raw materials for polyurethane foam are mainly derived from petroleum refining products, which are non-renewable resources. With global oil reserves becoming increasingly scarce, developing environmentally friendly polyurethane foam based on biomass raw materials has become an important direction for the industry. Currently, vegetable oils such as soybean oil, castor oil, corn oil, and sesame oil are used in the preparation of polyurethane foam materials to partially replace petroleum resources. However, the molecular structure of these vegetable oils is dominated by a large number of long-chain hydrocarbon groups, with a low proportion of flame-retardant elements. Their flammability is much higher than that of petroleum-based polyols, leading to a significant decrease in the flame-retardant performance of polyurethane foam materials. Although flame retardants can be added to improve its flame retardancy, this often sacrifices the material's mechanical properties. Furthermore, the market's requirements for the thermal insulation performance of foam materials are constantly increasing. At the same time, the porous and hydrophilic nature of polyurethane foam surfaces makes it susceptible to microbial contamination and erosion, affecting the stability of the material during use. Therefore, there is an urgent need to develop an environmentally friendly polyurethane foam material that can solve the above problems. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an environmentally friendly thermal insulation polyurethane foam material to address the shortcomings of the prior art, thereby improving the mechanical properties and flame retardant properties of polyurethane foam materials.

[0005] Another technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned environmentally friendly thermal insulation polyurethane foam material.

[0006] To solve the first technical problem mentioned above, the present invention discloses the following technical solution:

[0007] An environmentally friendly thermal insulation polyurethane foam material includes component A and component B; the mass ratio of component A to component B is 1:1; by weight, component A includes the following raw materials: 40-70 parts castor oil composite polyol, 20-40 parts polyether polyol, 5-10 parts functional diol, 1-3 parts foam stabilizer, 2-5 parts blowing agent, 0.5-2 parts catalyst, and 1-3 parts cell opener; component B is isocyanate; the castor oil composite polyol is composed of castor oil and castor oil-derived polyols in a mass ratio of 2:(1-1.5);

[0008] The structural formula of the functional diol is as follows:

[0009] .

[0010] Preferably, the preparation process of the castor oil-derived polyol includes the following steps:

[0011] Perfluoro-2,5-dimethyl-3,6-dioxane was added to dichloromethane, followed by the addition of 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. After stirring, L-cysteine ​​was added, and the mixture was reacted overnight at room temperature. After purification, intermediate 1 was obtained.

[0012] The structural formula of intermediate 1 is as follows:

[0013] ;

[0014] Intermediate 1, castor oil, and photoinitiator were added to anhydrous ethanol and reacted under ultraviolet light. After purification, the castor oil-derived polyol was obtained.

[0015] The structural formula of the castor oil-derived polyol is as follows:

[0016] .

[0017] The castor oil-derived polyol of this invention is prepared through a two-step reaction: first, perfluoro-2,5-dimethyl-3,6-dioxane-heptanoic acid is reacted with L-cysteine ​​to obtain intermediate 1; then, the thiol group at the end of intermediate 1 is reacted with castor oil, thereby introducing fluorinated segments and carboxylic acid groups into the polyol structure. The introduced fluoroalkyl group can significantly enhance the hydrophobicity of polyurethane foam; while the introduction of carboxylic acid groups increases reaction sites and improves the degree of crosslinking, thereby enhancing the mechanical strength of the material. In addition, the carboxylic acid group, as a synergistic catalyst in the water-blown foaming system, can regulate the CO2 release rate and, in synergy with the heterogeneous nucleation of pyridinium ions in the functional diol, refine the cell structure, forming a microporous system with a high closed-cell rate; simultaneously, the fluorinated segments and the long chain of castor oil provide hydrophobic barriers and toughness support, respectively, jointly reducing the risk of water vapor erosion and cell rupture, thereby effectively improving the thermal insulation performance and resilience of the material.

[0018] Preferably, the steps The molar ratio of perfluoro-2,5-dimethyl-3,6-dioxane-heptanoic acid, L-cysteine, 4-dimethylaminopyridine, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 15:(15-15.5):(20-25):(20-25); the stirring time is 30-45 min.

[0019] Preferably, the steps The molar ratio of castor oil, intermediate 1, and photoinitiator is 1:(3-3.2):(0.125-0.128); the photoinitiator is 2-hydroxy-2-methylphenylacetone; and the reaction time is 6-8 hours.

[0020] Preferably, the preparation process of the functional diol is as follows:

[0021] S1. Add 4-pyridinemethanol and triethylamine to dichloromethane, and add 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide in 2-3 portions at 0-5℃. React at room temperature and purify to obtain intermediate 2.

[0022] The structural formula of intermediate 2 is as follows:

[0023] ;

[0024] S2. The intermediate 2 and 4-bromobenzyl alcohol are added to acetonitrile, refluxed, and purified to obtain the functional diol.

[0025] This invention introduces a spirocyclic phosphoryl group into the molecular chain by reacting 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dioxide with 4-pyridinemethanol. The resulting intermediate 2 then undergoes a quaternization reaction with 4-bromobenzyl alcohol to introduce a benzyl group onto the pyridine nitrogen atom to form a pyridinium ion structure, ultimately obtaining a functional diol with both spirocyclic phosphoryl group and pyridinium ion structure.

[0026] Preferably, in step S1, the ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 4-pyridinemethanol, and triethylamine is 5 mmol:(12-18) mmol:(5-8) mL; and the reaction time is 36-60 h.

[0027] Preferably, the molar ratio of 4-bromobenzyl alcohol and intermediate 2 in step S2 is (2.5-3):1; and the reflux reaction time is 36-60 h.

[0028] Preferably, the polyether polyol is selected from CHE-330N, CHE-628, and CHE-210; and the isocyanate is selected from toluene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.

[0029] Preferably, the foam stabilizer is Momentive L580 or Momentive L-3881; the catalyst is selected from one of dibutyltin dilaurate, stannous octoate, triethylenediamine, and dimethylaminoethyl ether; the cell opener is GK-350D; and the foaming agent is water.

[0030] To solve the second technical problem mentioned above, the present invention discloses the following technical solution:

[0031] The preparation method of the above-mentioned environmentally friendly thermal insulation polyurethane foam material includes the following steps:

[0032] (a) Weigh component A according to the stated weight proportions and mix them evenly to obtain component A;

[0033] (b) Add components A and B to the material cylinder respectively, and control the material temperature at 23-26℃. Mix components A and B at the nozzle according to the mass ratio, foam for 100-150 seconds, and then mature for 7-9 hours.

[0034] The beneficial technical effects of this invention are as follows:

[0035] (1) The environmentally friendly thermal insulation polyurethane foam material of the present invention achieves an optimized balance between mechanical strength and flame retardant performance. It not only has high structural support strength, but also effectively improves the fire safety level.

[0036] (2) The addition of functional diols in this invention can significantly improve the flame retardant and antibacterial properties of the material. The flame retardant mechanism of the functional diols in this invention is a synergistic effect of phosphorus-nitrogen-carbon, achieving high-efficiency flame retardancy through the triple action of charring shielding, gas phase dilution, and free radical capture: the spirocyclic phosphate ester in the molecule decomposes upon heating to produce active phosphoric acid, which catalyzes the deep dehydration of the polymer and its own aromatic ring (phenyl and pentaerythritol skeleton) to form a dense and continuous char layer; the pyridinium structure releases non-combustible gases such as N2 / NH3, making the char layer expand and porous, effectively isolating heat and oxygen; phosphorus free radicals (PO / PO2) capture H / OH to interrupt the combustion chain reaction; nitrogen and phosphorus produce PN synergistic effect, improving charring efficiency and char layer thermal stability. In addition, the pyridinium ions in the functional diols also endow the material with excellent antibacterial properties.

[0037] (3) This invention also improves the thermal insulation performance, resilience, and mechanical properties of the material by adding castor oil-derived polyols. Specifically, the fluoroalkyl groups introduced into the castor oil-derived polyols of this invention can significantly enhance the hydrophobicity of polyurethane foam, while the introduction of carboxylic acid groups increases reaction sites and improves the degree of crosslinking, thereby enhancing the mechanical strength of the material. In addition, the carboxylic acid groups, as synergistic catalysts in the water-blown foaming system, can regulate the CO2 release rate and, together with the heterogeneous nucleation of pyridinium ions in the functional diols, refine the cell structure, forming a microporous system with a high closed-cell rate; at the same time, the fluorinated segments and the long castor oil chains provide hydrophobic barriers and toughness support, respectively, jointly reducing the risk of water vapor erosion and cell rupture, thereby effectively improving the thermal insulation performance and resilience of the material. Detailed Implementation

[0038] The following is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention. Specific conditions not specified in the embodiments are performed according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, all reagents or instruments used are conventional products obtained through commercial channels.

[0039] Example 1

[0040] A castor oil-derived polyol is prepared as follows:

[0041] ,

[0042] In the formula, R= .

[0043] A mixture of perfluoro-2,5-dimethyl-3,6-dioxane, L-cysteine, 4-dimethylaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and dichloromethane was prepared in a ratio of 15 mmol:15.3 mmol:22 mmol:24 mmol:160 mL. Perfluoro-2,5-dimethyl-3,6-dioxane (CAS:2479-73-4) was added to dichloromethane, followed by the addition of 4-dioxane. After stirring methylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (CAS: 7084-11-9) for 40 min, L-cysteine ​​was added, and the mixture was reacted overnight at room temperature. After the reaction was complete, dichloromethane was added for dilution, followed by washing with deionized water and saturated brine, drying with anhydrous MgSO4, evaporating under reduced pressure, and purifying by column chromatography to obtain intermediate 1 (yield 78.6%). The NMR and mass spectrometry results of intermediate 1 are as follows:

[0044] 1 HNMR: (C 10 H6F 13 SNO5, 400MHz, DMSO- d6 ) δ: 1.4 (s, 1H), 2.90-2.94 (m, 1H), 3.15-3.19 (m, 1H), 4.76-4.80 (t, 1H), 8.32 (s, 1H), 12.39 (s, 1H). MS (ESI) m / z=498.98[M].

[0045] Castor oil, intermediate 1, 2-hydroxy-2-methylphenylacetone, and anhydrous ethanol were added to anhydrous ethanol in a ratio of 0.1 mol: 0.31 mol: 0.0126 mol: 135 mL. The intermediate 1, castor oil, and 2-hydroxy-2-methylphenylacetone (CAS: 7473-98-5) were reacted under a 1000 W UV lamp for 7 h. After the reaction was complete, the mixture was concentrated by rotary evaporation and purified by column chromatography to obtain the castor oil-derived polyol (yield 83.5%). The NMR and mass spectrometry results of the castor oil-derived polyol are as follows:

[0046] 1 HNMR: (C 87 H 122 O 24 S3F 39 N3, 400MHz, DMSO- d6 ) δ: 0.86-0.90 (m, 9H), 1.23-1.28 (m, 36H), 1.28-1.35 (m, 12H), 1.38-1.42 (m, 12H), 1.56-1.60 (m, 12H), 1.64-1.68 (m, 6H), 2.30-2.36 (m, 9H), 2.79- 2.83 (m, 3H), 3.04-3.08 (m, 3H), 3.38-3.42 (m, 3H), 4.28-4.32 (d, 4H), 4.7 2-4.76 (t, 3H), 4.8 (s, 3H), 5.83-5.87 (m, 1H), 8.32 (s, 3H), 12.39 (s, 3H). MS (ESI) m / z=2429.70 [M].

[0047] Example 2

[0048] A castor oil-derived polyol is prepared as follows:

[0049] Using perfluoro-2,5-dimethyl-3,6-dioxane, L-cysteine, 4-dimethylaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and dichloromethane in a ratio of 15 mmol:15 mmol:20 mmol:20 mmol:150 mL, perfluoro-2,5-dimethyl-3,6-dioxane was added to dichloromethane, followed by the addition of 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. After stirring for 30 min, L-cysteine ​​was added, and the mixture was reacted overnight at room temperature. After the reaction was complete, the mixture was diluted with dichloromethane, washed successively with deionized water and saturated brine, dried over anhydrous MgSO4, evaporated under reduced pressure, and purified by column chromatography to obtain intermediate 1 (yield 77.1%). The NMR and mass spectrometry results of intermediate 1 were the same as in Example 1.

[0050] Castor oil, intermediate 1, 2-hydroxy-2-methylphenylacetone, and anhydrous ethanol were added to anhydrous ethanol in a ratio of 0.1 mol: 0.3 mol: 0.0125 mol: 125 mL. The mixture was reacted under a 1000 W UV lamp for 6 h. After the reaction was completed, the mixture was concentrated by rotary evaporation and purified by column chromatography to obtain the castor oil-derived polyol (yield 82.8%). The NMR and mass spectrometry results of the castor oil-derived polyol were the same as in Example 1.

[0051] Example 3

[0052] A castor oil-derived polyol is prepared as follows:

[0053] Using perfluoro-2,5-dimethyl-3,6-dioxane, L-cysteine, 4-dimethylaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and dichloromethane in a ratio of 15 mmol:15.5 mmol:25 mmol:25 mmol:200 mL, perfluoro-2,5-dimethyl-3,6-dioxane was added to dichloromethane, followed by the addition of 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. After stirring for 45 min, L-cysteine ​​was added, and the mixture was reacted overnight at room temperature. After the reaction was complete, the mixture was diluted with dichloromethane, washed successively with deionized water and saturated brine, dried over anhydrous MgSO4, evaporated under reduced pressure, and purified by column chromatography to obtain intermediate 1 (yield 76.7%). The NMR and mass spectrometry results of intermediate 1 were the same as in Example 1.

[0054] Castor oil, intermediate 1, 2-hydroxy-2-methylphenylacetone, and anhydrous ethanol were added to anhydrous ethanol in a ratio of 0.1 mol: 0.32 mol: 0.0128 mol: 150 mL. The mixture was reacted under a 1000 W UV lamp for 8 h. After the reaction was completed, the mixture was concentrated by rotary evaporation and purified by column chromatography to obtain the castor oil-derived polyol (yield 81.4%). The NMR and mass spectrometry results of the castor oil-derived polyol were the same as in Example 1.

[0055] Example 4

[0056] A functional polyol is prepared as follows:

[0057] ;

[0058] S1. Using 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane 3,9-dioxide, 4-pyridinemethanol, triethylamine, and dichloromethane in a ratio of 5 mmol:16 mmol:7 mL:90 mL, 4-pyridinemethanol and triethylamine were added to dichloromethane. 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane 3,9-dioxide (CAS: 714-87-4) was added in two portions at 4 °C. The reaction was carried out at room temperature for 50 h. After the reaction was complete, the reaction solution was washed with water, the organic phase was dried over anhydrous magnesium sulfate, concentrated by rotary evaporation, and purified by column chromatography to obtain intermediate 2 (yield 73.4%). The NMR and mass spectrometry results of intermediate 2 are as follows:

[0059] 1 HNMR: (C 17 H 20 N₂O₈P₂, 400MHz, DMSO- d6 ) δ: 3.87-3.91 (d, 8H), 6.05-6.09 (d, 4H), 7.44-7.48 (d, 4H), 8.60-8.64 (d, 4H). MS (ESI) m / z=442.07 [M].

[0060] S2. Intermediate 2 and 4-bromobenzyl alcohol were added to acetonitrile at a ratio of 11 mmol:4 mmol:55 mL, and the mixture was refluxed for 50 h. After the reaction was complete, the reaction solution was cooled to room temperature, filtered to obtain a solid product, washed with acetonitrile, and dried under vacuum to obtain a functionalized diol (yield 80.6%). The NMR and mass spectrometry results of the functionalized diol are as follows:

[0061] 1 HNMR: (C 31 H 34 N2O10 P2 2+ 400MHz, DMSO- d6 ) δ: 3.87-3.91 (d, 8H), 4.61 (s, 4H), 5.27 (s, 2H), 5.29 (s, 4H), 7.26-7.30 (d, 4H), 7.85-7.89 (d, 4H), 8.17-8.21 (d, 4H), 8.76-8.80 (d, 4H). MS (ESI) m / z=656.17 [M].

[0062] Example 5

[0063] A functional polyol is prepared as follows:

[0064] S1. Using 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane 3,9-dioxide, 4-pyridinemethanol, triethylamine, and dichloromethane in a ratio of 5 mmol:12 mmol:5 mL:80 mL, 4-pyridinemethanol and triethylamine were added to dichloromethane. 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane 3,9-dioxide was added in three portions at 0 °C. The reaction was carried out at room temperature for 36 h. After the reaction was completed, the reaction solution was washed with water, the organic phase was dried with anhydrous magnesium sulfate, concentrated by rotary evaporation, and purified by column chromatography to obtain intermediate 2 (yield 71.8%). The NMR and mass spectrometry results of intermediate 2 were the same as in Example 4.

[0065] S2. With a ratio of 10 mmol:4 mmol:50 mL for 4-bromobenzyl alcohol, intermediate 2, and acetonitrile, intermediate 2 and 4-bromobenzyl alcohol were added to acetonitrile, and the mixture was refluxed for 36 h. After the reaction was completed, the reaction solution was cooled to room temperature, filtered to obtain a solid product, washed with acetonitrile, and dried under vacuum to obtain a functional diol (yield 78.4%). The NMR and mass spectrometry results of the functional diol were the same as in Example 4.

[0066] Example 6

[0067] A functional polyol is prepared as follows:

[0068] S1. Using 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane 3,9-dioxide, 4-pyridinemethanol, triethylamine, and dichloromethane in a ratio of 5 mmol:18 mmol:8 mL:100 mL, 4-pyridinemethanol and triethylamine were added to dichloromethane. 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane 3,9-dioxide was added in three portions at 5 °C. The reaction was carried out at room temperature for 60 h. After the reaction was completed, the reaction solution was washed with water, the organic phase was dried with anhydrous magnesium sulfate, concentrated by rotary evaporation, and purified by column chromatography to obtain intermediate 2 (yield 71.9%). The NMR and mass spectrometry results of intermediate 2 were the same as in Example 4.

[0069] S2. With a molar ratio of 4-bromobenzyl alcohol, intermediate 2, and acetonitrile of 12 mmol:4 mmol:60 mL, intermediate 2 and 4-bromobenzyl alcohol were added to acetonitrile, and the mixture was refluxed for 60 h. After the reaction was completed, the reaction solution was cooled to room temperature, filtered to obtain a solid product, washed with acetonitrile, and dried under vacuum to obtain a functional diol (yield 78.2%). The NMR and mass spectrometry results of the functional diol were the same as in Example 4.

[0070] Example 7

[0071] An environmentally friendly thermal insulation polyurethane foam material, comprising component A and component B in a mass ratio of 1:1.

[0072] Component B is toluene diisocyanate;

[0073] By weight, component A comprises the following raw materials: 60 parts castor oil complex polyol, 30 parts CHE-330N, 7 parts functional diol from Example 4, 2 parts Momentive L580, 4 parts water, 1 part dibutyltin dilaurate, and 2 parts GK-350D; wherein the castor oil complex polyol is composed of castor oil and castor oil-derived polyol from Example 1 in a mass ratio of 2:1.2.

[0074] The preparation method of the above-mentioned environmentally friendly thermal insulation polyurethane foam material includes the following steps:

[0075] (a) Weigh out component A according to the above-mentioned weight proportions and mix them evenly to obtain component A;

[0076] (b) Add component A and component B to the material cylinder respectively, and control the material temperature at 25°C. Mix component A and component B at the foaming gun head according to the above mass ratio, and convey them to the foaming continuous line for foaming for 120 seconds. Let it mature at room temperature for 8 hours.

[0077] Example 8

[0078] An environmentally friendly thermal insulation polyurethane foam material, comprising component A and component B in a mass ratio of 1:1.

[0079] Component B is isophorone diisocyanate;

[0080] By weight, component A comprises the following raw materials: 40 parts castor oil complex polyol, 20 parts CHE-628, 5 parts functional diol from Example 5, 1 part Momentive L-3881, 2 parts water, 0.5 parts stannous octoate, and 1 part GK-350D; wherein the castor oil complex polyol is composed of castor oil and castor oil-derived polyol from Example 2 in a mass ratio of 2:1.

[0081] The preparation method of the above-mentioned environmentally friendly thermal insulation polyurethane foam material includes the following steps:

[0082] (a) Weigh out component A according to the above-mentioned weight proportions and mix them evenly to obtain component A;

[0083] (b) Add component A and component B to the material cylinder respectively, and control the material temperature at 23°C. Mix component A and component B at the foaming gun head according to the above mass ratio, and convey them to the foaming continuous line for foaming for 100 seconds. Let it mature at room temperature for 7 hours.

[0084] Example 9

[0085] An environmentally friendly thermal insulation polyurethane foam material, comprising component A and component B in a mass ratio of 1:1.

[0086] Component B is diphenylmethane diisocyanate;

[0087] By weight, component A comprises the following raw materials: 70 parts castor oil complex polyol, 40 parts CHE-210, 10 parts functional diol from Example 6, 3 parts Momentive L-3881, 5 parts water, 2 parts triethylenediamine, and 3 parts GK-350D; wherein the castor oil complex polyol is composed of castor oil and castor oil-derived polyol from Example 3 in a mass ratio of 2:1.5.

[0088] The preparation method of the above-mentioned environmentally friendly thermal insulation polyurethane foam material includes the following steps:

[0089] (a) Weigh out component A according to the above-mentioned weight proportions and mix them evenly to obtain component A;

[0090] (b) Add component A and component B to the material cylinder respectively, and control the material temperature at 26°C. Mix component A and component B at the foaming gun head according to the above mass ratio, and convey them to the foaming continuous line for foaming for 150 seconds. Then, let them mature at room temperature for 9 hours.

[0091] Comparative Example 1

[0092] The difference between Comparative Example 1 and Example 7 is that the functional diol of Example 4 was not added to component A, while the rest is the same as in Example 7.

[0093] Comparative Example 2

[0094] The difference between Comparative Example 2 and Example 7 is that castor oil is used instead of castor oil complex polyol in component A, while the rest is the same as in Example 7.

[0095] The properties of the polyurethane foam materials obtained in Examples 7-9 and Comparative Examples 1-2 of this invention are described below.

[0096] Antibacterial activity: The antibacterial activity of each material against Staphylococcus aureus and Escherichia coli was tested according to WS / T650-2019. The experimental results are shown in Table 1.

[0097] Resilience: The resilience of each material was tested according to GB / T6670-2008, and the experimental results are shown in Table 1.

[0098] Flame retardant performance: The limiting oxygen index of each material was tested according to GB / T2406.2-2009, and the experimental results are shown in Table 1.

[0099] Mechanical properties: The tensile strength and elongation at break of each material were tested according to GB / T6344-2008. The experimental results are shown in Table 1.

[0100] Thermal insulation: The thermal conductivity of each material was tested according to GB / T10295-2008, and the experimental results are shown in Table 1.

[0101] Table 1

[0102] Groups / Indicators Antibacterial activity of Escherichia coli / % Antibacterial activity of Staphylococcus aureus / % Rebound rate / % Limiting oxygen index / % Tensile strength / KPa Elongation at break / % Thermal conductivity / mW / (m·K) Example 7 99.6 98.9 66.7 34.1 161 192 16.5 Example 8 99.5 98.9 66.3 33.9 158 188 16.3 Example 9 99.6 98.7 66.1 33.5 156 185 16.2 Comparative Example 1 8.3 9.6 64.8 22.4 154 187 17.6 Comparative Example 2 99.1 98.4 58.5 32.7 142 166 24.1

[0103] As shown in Table 1, compared with Comparative Example 1, the material prepared in Example 1 exhibits superior flame retardant and antibacterial properties. The experimental data above demonstrate that the addition of functional diols significantly enhances the flame retardant and antibacterial properties of the material. The flame retardant mechanism of the functional diols in this invention is a synergistic effect of phosphorus-nitrogen-carbon, achieving high-efficiency flame retardancy through a triple action of char formation shielding, gas-phase dilution, and free radical capture: the spirocyclic phosphate ester in the molecule decomposes upon heating to produce active phosphoric acid, catalyzing deep dehydration of the polymer and its own aromatic rings (phenyl and pentaerythritol skeleton), forming a dense and continuous char layer; the pyridinium structure releases non-combustible gases such as N2 / NH3, causing the char layer to expand and become porous, effectively isolating heat and oxygen; phosphorus free radicals (PO / PO2) capture H / OH, interrupting the combustion chain reaction; nitrogen and phosphorus produce a synergistic effect of PN, improving char formation efficiency and char layer thermal stability. Furthermore, the pyridinium ions in the functional diols also endow the material with excellent antibacterial properties.

[0104] Compared to Comparative Example 2, the material prepared in Example 1 exhibits superior thermal insulation, resilience, and mechanical properties. The experimental data above demonstrates that the addition of castor oil-derived polyols significantly improves the thermal insulation, resilience, and mechanical properties of the material. Specifically, the fluoroalkyl groups introduced into the castor oil-derived polyols of this invention significantly enhance the hydrophobicity of the polyurethane foam, while the introduction of carboxylic acid groups increases reaction sites and improves the degree of crosslinking, thereby enhancing the mechanical strength of the material. Furthermore, the carboxylic acid groups, acting as a synergistic catalyst in the water-blowing system, can regulate the CO2 release rate and, in conjunction with the heterogeneous nucleation of pyridinium ions in the functional diols, refine the cell structure, forming a high-closed-pore microporous system. Simultaneously, the fluorinated segments and the long castor oil chains provide a hydrophobic barrier and toughness support, respectively, jointly reducing the risk of water vapor erosion and cell rupture, thus effectively improving the thermal insulation and resilience of the material.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. The basic principles and main features of the present invention have been described above with specific implementation schemes. Based on the present invention, some modifications or substitutions can be made, but these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of protection claimed by the present invention.

Claims

1. An environmentally friendly thermal insulation polyurethane foam material, characterized in that, It includes component A and component B; the mass ratio of component A to component B is 1:1; by weight, component A includes the following raw materials: 40-70 parts of castor oil complex polyol, 20-40 parts of polyether polyol, 5-10 parts of functional diol, 1-3 parts of foam stabilizer, 2-5 parts of foaming agent, 0.5-2 parts of catalyst, and 1-3 parts of cell opener; component B is isocyanate; the castor oil complex polyol is composed of castor oil and castor oil-derived polyols in a mass ratio of 2:(1-1.5); The structural formula of the functional diol is as follows: ； The structural formula of the castor oil-derived polyol is as follows: 。 2. The environmentally friendly thermal insulation polyurethane foam material according to claim 1, characterized in that, The preparation process of the castor oil-derived polyol includes the following steps: Perfluoro-2,5-dimethyl-3,6-dioxane was added to dichloromethane, followed by the addition of 4-dimethylaminopyridine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. After stirring, L-cysteine ​​was added, and the mixture was reacted overnight at room temperature. After purification, intermediate 1 was obtained. The structural formula of intermediate 1 is as follows: ； Intermediate 1, castor oil, and photoinitiator were added to anhydrous ethanol and reacted under ultraviolet light. After purification, the castor oil-derived polyol was obtained.

3. The environmentally friendly thermal insulation polyurethane foam material according to claim 2, characterized in that, step The molar ratio of perfluoro-2,5-dimethyl-3,6-dioxane-heptanoic acid, L-cysteine, 4-dimethylaminopyridine, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride is 15:(15-15.5):(20-25):(20-25); the stirring time is 30-45 min.

4. The environmentally friendly thermal insulation polyurethane foam material according to claim 2, characterized in that, step The molar ratio of castor oil, intermediate 1, and photoinitiator is 1:(3-3.2):(0.125-0.128); the photoinitiator is 2-hydroxy-2-methylphenylacetone; and the reaction time is 6-8 hours.

5. The environmentally friendly thermal insulation polyurethane foam material according to claim 1, characterized in that, The preparation process of the functional diol is as follows: S1. Add 4-pyridinemethanol and triethylamine to dichloromethane, and add 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide in 2-3 portions at 0-5℃. React at room temperature and purify to obtain intermediate 2. The structural formula of intermediate 2 is as follows: ； S2. The intermediate 2 and 4-bromobenzyl alcohol are added to acetonitrile, refluxed, and purified to obtain the functional diol.

6. The environmentally friendly thermal insulation polyurethane foam material according to claim 5, characterized in that, In step S1, the ratio of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide, 4-pyridinemethanol, and triethylamine is 5 mmol: (12-18) mmol: (5-8) mL; the reaction time is 36-60 h.

7. The environmentally friendly thermal insulation polyurethane foam material according to claim 5, characterized in that, In step S2, the molar ratio of 4-bromobenzyl alcohol to intermediate 2 is (2.5-3):1; the reflux reaction time is 36-60 h.

8. The environmentally friendly thermal insulation polyurethane foam material according to claim 1, characterized in that, The polyether polyol is selected from CHE-330N, CHE-628, and CHE-210; the isocyanate is selected from toluene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.

9. The environmentally friendly thermal insulation polyurethane foam material according to claim 1, characterized in that, The foam stabilizer is Momentive L580 or Momentive L-3881; the catalyst is selected from one of dibutyltin dilaurate, stannous octoate, triethylenediamine, and dimethylaminoethyl ether; the cell opener is GK-350D; and the foaming agent is water.

10. A method for preparing the environmentally friendly thermal insulation polyurethane foam material according to any one of claims 1-9, characterized in that, Includes the following steps: (a) Weigh component A according to the stated weight proportions and mix them evenly to obtain component A; (b) Add components A and B to the material cylinder respectively, and control the material temperature at 23-26℃. Mix components A and B at the nozzle according to the mass ratio, foam for 100-150 seconds, and then mature for 7-9 hours.

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