Flame-retardant polyol as well as preparation method and application thereof
By preparing P-Si-OH flame-retardant polyols with active terminal hydroxyl groups, the problems of insufficient flame retardancy and mechanical properties of flexible polyurethane foam materials were solved, and the flame retardancy and mechanical properties of the materials were improved. In particular, the materials exhibited excellent toughness and migration resistance in applications such as seat cushions.
Patent Information
- Application Number
- CN202411167699.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-23
- Publication Date
- 2026-03-03
AI Technical Summary
Existing flexible polyurethane foam materials have shortcomings in terms of flame retardancy and mechanical properties, especially in applications such as seat cushions, where it is difficult to achieve both high flame retardancy and excellent toughness.
A flame-retardant polyol of Formula I is used, which is prepared by reacting diphenylphosphine chloride with triol, silicon source and diol to generate P-Si-OH with two active terminal hydroxyl groups, which participates in the foaming and gelation process of polyurethane foam. The low-valence phosphorus element and silicon-oxygen bond are used to improve flame retardancy and mechanical properties.
It achieves high flame retardancy and migration resistance in polyurethane foam materials, significantly improves tensile strength and elongation at break, reduces compression set, and maintains good mechanical properties.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of flame retardant technology, specifically to a flame-retardant polyol, its preparation method, and its application. Background Technology
[0002] Flexible polyurethane foam (FPUF) is widely used in the preparation of cushioning, decorative, and thermal insulation materials due to its advantages such as lightweight, thermal insulation, and high mechanical elasticity. However, due to its high flammability, it will burn rapidly under ignition conditions, producing a large number of molten droplets, accompanied by the release of a large amount of heat and toxic fumes, seriously threatening human life and property safety. Therefore, flame retardancy is essential.
[0003] Currently, there are three main methods for flame retardant treatment of FPUF materials: impregnation flame retardancy, addition of flame retardants, and reactive flame retardancy. Impregnation flame retardancy typically requires a large impregnation volume, which not only damages the mechanical properties of FPUF but also causes environmental pollution due to the large amount of water used. Adding flame retardants generally involves adding compounds containing phosphorus, chlorine, bromine, antimony, aluminum, boron, nitrogen, etc., which have flame-retardant properties but do not contain reactive groups, to FPUF, giving the product flame-retardant properties. However, halogen-containing flame retardants have been banned in recent years, and phosphorus-containing small-molecule flame retardants, due to their large addition amounts, reduce the mechanical properties of FPUF. Furthermore, over time, these flame retardants migrate and precipitate as the material ages, further reducing its flame-retardant and mechanical properties during use. Reactive flame retardancy generally uses polyhydroxy compounds containing flame-retardant elements as flame retardants. These flame retardants can participate in the macromolecular chain of FPUF through covalent bonds, thus effectively overcoming the shortcomings of impregnation and addition of flame retardants.
[0004] Currently, some phosphorus / phosphonic polyols have been developed as reactive flame retardants, but most of them remain inefficient in delaying combustion and achieving self-extinguishing. Furthermore, toughness is also a crucial property for FPUFs, such as in applications like seat cushions. Therefore, developing FPUFs with high flame retardancy while also possessing excellent strength and toughness remains a pressing issue. Summary of the Invention
[0005] In view of this, the purpose of this invention is to provide a flame-retardant polyol, its preparation method, and its application. The flame-retardant polyol can endow FPUF with excellent high flame retardancy, high fire safety, and mechanical properties.
[0006] To achieve this objective, the present invention adopts the following technical solution:
[0007] In a first aspect, the present invention provides a flame-retardant polyol of Formula I:
[0008] Formula I;
[0009] Wherein, R1 is selected from hydrogen, substituted or unsubstituted C1-C6 alkyl groups, and R2 is selected from -(CH2). m -, m can be any integer from 2 to 6;
[0010] n can be any integer from 1 to 4.
[0011] Preferably, R1 is selected from hydrogen, substituted or unsubstituted C1-C3 alkyl groups.
[0012] Preferably, m is 2 or 3.
[0013] Preferably, the flame-retardant polyol is selected from any one of the following formulas:
[0014] .
[0015] Secondly, the present invention provides a method for preparing the above-mentioned flame-retardant polyol, comprising the following steps:
[0016] S1: Reaction of diphenylphosphine chloride with an acid-binding agent and a mixture of triols represented by formula A yields the first intermediate;
[0017] S2: React the first intermediate, silicon source, and acid-binding agent to obtain the second intermediate;
[0018] S3: React the second intermediate with the diol shown in Formula B to obtain the flame-retardant polyol shown in Formula I;
[0019] Formula A; Formula B;
[0020] Wherein, R1 is selected from hydrogen, substituted or unsubstituted C1-C6 alkyl groups, and R2 is selected from -(CH2). m -, m can be any integer from 2 to 6.
[0021] Preferably, the molar ratio of the diphenylphosphine chloride, the triol of formula A, the silicon source, and the diol of formula B is 1:(1~1.5):(1~2.5):(1~4).
[0022] Preferably, the acid-binding agent in step S1 or step S2 is selected from any one or more of triethylamine, pyridine / or imidazole.
[0023] Preferably, the silicon source is selected from dichlorodimethylsilane.
[0024] Preferably, the reaction in step S1 is carried out in the presence of a solvent selected from one or more of tetrahydrofuran, chloroform, acetonitrile, dichloromethane, N,N-dimethylformamide, or dimethylacetamide.
[0025] Preferably, the reaction described in step S1 is carried out at 0~10℃ for 0.5~72 h, and then the temperature is raised to 30~70℃ for another 0.5~72 h.
[0026] Preferably, the reaction described in step S2 is carried out at 0~10℃ for 0.5~72 h, and then the temperature is raised to 30~70℃ for another 0.5~72 h.
[0027] Preferably, the reaction temperature in step S3 is 30~70℃ and the reaction time is 0.5~72 h.
[0028] Preferably, the reactions in steps S1, S2, and S3 are all carried out under an inert atmosphere.
[0029] Preferably, the first intermediate in step S2 undergoes the following processing:
[0030] The first intermediate was mixed with a solvent, washed, and then subjected to rotary evaporation and drying to obtain a viscous liquid.
[0031] Preferably, the solvent is selected from dichloromethane and / or chloroform.
[0032] Thirdly, the present invention provides a polyurethane foam material comprising isocyanate and polyol;
[0033] The polyols include polyether polyols and flame-retardant polyols involved in the above technical solutions.
[0034] Preferably, the flame-retardant polyol is 10-20 parts by weight, based on 100 parts by weight of the polyether polyol.
[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0036] This invention provides a flame-retardant polyol of Formula I (referred to as "P-Si-OH"), which has two active terminal hydroxyl groups. Compared with existing small-molecule phosphate flame retardants, the flame-retardant polyol P-Si-OH prepared by this invention has two active terminal hydroxyl groups that can react with isocyanates, thereby enabling it to participate in the foaming and gelation process of FPUF, which can effectively improve the migration resistance of the flame retardant. Simultaneously, the low-valence phosphorus element in P-Si-OH can play a gas-phase flame-retardant role during combustion, thus endowing FPUF with high flame retardancy and migration resistance.
[0037] Testing showed that the FPUF material prepared using the flame-retardant polyol and polyether polyol provided in this invention exhibits excellent flame-retardant properties. When 10% P-Si-OH of the polyether polyol is added, it passes the vertical burning Cal TB117 test and continues to pass the test after a heat aging experiment at 140℃ for 22 hours. Its tensile strength increases from 145 kPa to 214 kPa, and its elongation at break increases from 132% to 186%. After 100 cycles of compression, its strength recovery rate and deformation recovery rate are essentially consistent with those of pure FPUF. The compression set at 70℃ with 50% permanent compression set is only 4.9%. Attached Figure Description
[0038] Figure 1 The flame-retardant polyol obtained in Example 1 31 P NMR spectrum;
[0039] Figure 2 The flame-retardant polyol obtained in Example 1 1 H NMR spectrum. Detailed Implementation
[0040] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0041] To address the issue that existing FPUF materials cannot simultaneously achieve excellent flame retardancy and mechanical properties, this invention provides a flame-retardant polyol represented by Formula I:
[0042] Formula I;
[0043] Wherein, R1 is selected from hydrogen, substituted or unsubstituted C1~C6 alkyl groups, and R2 is selected from substituted or unsubstituted C1~C6 alkyl groups; n represents the degree of polymerization, which can be an integer from 1 to 4, such as 1, 2, 3 or 4.
[0044] In some embodiments of the present invention, the flame-retardant polyol has the structure shown in Formula I, wherein R1 is preferably derived from hydrogen, substituted or unsubstituted C1-C3 alkyl groups, more preferably methyl; and R2 is preferably derived from substituted or unsubstituted C1-C3 alkyl groups.
[0045] In this invention, the "substituted" group in "substituted or unsubstituted" is selected from the isopropyl group.
[0046] In some specific embodiments of the present invention, the flame-retardant polyol is selected from any one of the following formulas:
[0047] .
[0048] The flame-retardant polyol of Formula I provided by this invention has two active terminal hydroxyl groups, which can participate in the foaming and gelation process of FPUF. The low-valence phosphorus can capture hydrogen free radicals and hydroxyl free radicals generated during the combustion of FPUF, thereby blocking the chain reaction of combustion and giving FPUF high flame-retardant properties. The presence of silicon-oxygen bonds can increase the flexibility of the molecular chain in FPUF, and the phosphorus-oxygen bonds in P-Si-OH can form hydrogen bonds with urethane, thereby giving FPUF high tensile properties and good compressibility and resilience.
[0049] The present invention also provides a method for preparing the above-mentioned flame-retardant polyol, which includes the following steps:
[0050] S1: After reacting diphenylphosphine chloride with a mixture of triol and acid-binding agent as shown in Formula A, the mixture is filtered to obtain the first intermediate;
[0051] S2: React the first intermediate, silicon source, and acid-binding agent to obtain the second intermediate;
[0052] S3: React the second intermediate with the diol shown in Formula B to obtain the flame-retardant polyol shown in Formula I;
[0053] Formula A; Formula B;
[0054] Wherein, R1 is selected from hydrogen, substituted or unsubstituted C1 to C6 alkyl groups, and R2 is selected from substituted or unsubstituted C1 to C6 alkyl groups.
[0055] The specific synthetic route in this preparation method is as follows:
[0056] In a three-necked flask, 0.2 mol (18.4 g) of glycerol was dispersed in 100 mL of anhydrous tetrahydrofuran, and 0.21 mol (21.2 g) of triethylamine was added. 0.2 mol (47.3 g) of diphenylphosphine chloride was dissolved in 100 mL of tetrahydrofuran. The solutions were added dropwise to the three-necked flask through a dropping funnel under a nitrogen atmosphere and in an ice-water bath at 0 °C. The mixture was stirred for 1 h, then heated to 50 °C and reacted for 3 h. Triethylamine hydrochloride was removed by filtration, and tetrahydrofuran was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and excess triethylamine hydrochloride was removed by repeated extraction with 50 mL of saturated NaHCO3 aqueous solution and deionized water. Dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 80 °C for 12 h to obtain a viscous liquid a.
[0057] Under ice bath conditions, 0.4 mol (51.6 g) of dichlorodimethylsilane, 0.9 mol (91.1 g) of triethylamine, and anhydrous tetrahydrofuran were added to a three-necked flask. 0.2 mol (58.6 g) of a dissolved in 100 mL of anhydrous tetrahydrofuran was added dropwise to the flask. The reaction was carried out in an ice bath for 1 h, then heated to 50 °C for 3 h. 0.21 mol of 1,4-butanediol (19.1 g) was added dropwise through a dropping funnel and reacted for 5 h. Triethylamine hydrochloride was removed by filtration, and tetrahydrofuran was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and excess triethylamine hydrochloride was removed by repeated extraction with 50 mL of saturated NaHCO3 aqueous solution and deionized water. Dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 80 °C for 12 h to obtain a viscous liquid polyol, P-Si-OH.
[0058]
[0059] It should be noted that since the above synthesis process is a condensation reaction, the value of n in the final flame-retardant polyol shown in Formula I is not unique. That is, in the flame-retardant polyol obtained, n can be any combination of 1, 2, 3, and 4 in the corresponding Formula I.
[0060] According to the present invention, a mixture of diphenylphosphine chloride and a triol of formula A and an acid-binding agent is first reacted and then filtered to obtain a first intermediate. In this reaction, the phosphonic chloride of the diphenylphosphine chloride reacts with the hydroxyl group of the triol to generate a diol containing a diphenylphosphine ester structure, and simultaneously generates hydrogen chloride (i.e., hydrochloric acid) as a byproduct. The present invention preferably adds an acid-binding agent selected from triethylamine and / or imidazole, which can react with hydrochloric acid and precipitate it, shifting the reaction equilibrium to the right, thereby increasing the product yield. In the present invention, this reaction step is preferably carried out in the presence of a solvent selected from one or more of tetrahydrofuran, chloroform, acetonitrile, dichloromethane, N,N-dimethylformamide, or dimethylacetamide. Furthermore, to prevent the phosphonic chloride in the diphenylphosphine chloride from reacting with water in the air beforehand, the present invention preferably carries out the reaction under an inert atmosphere. The inert atmosphere can be any atmosphere known to those skilled in the art; nitrogen is preferred in the present invention.
[0061] In some embodiments of the present invention, it is preferred to mix the triol, solvent, and acid-binding agent evenly to prepare solution A; and to mix diphenylphosphine chloride with the solvent evenly to obtain solution B. Then, solutions A and B are mixed, preferably reacted at 0-10°C for 0.5-72 h, followed by a reaction at 30-70°C for 0.5-72 h, or preferably reacted at 0°C (ice-water bath conditions) for 1-24 h, followed by a reaction at 50°C for 3-48 h. The present invention employs a reaction configuration of low temperature followed by high temperature, which effectively reduces the reaction rate and the heat released during the low-temperature dropwise addition. Heating after the dropwise addition is complete promotes the reaction. It should be noted that in the present invention, the molar ratio of diphenylphosphine chloride to the triol represented by formula A is 1:(1-1.5), preferably 1:(1-1.2), and more preferably 1:1. The amount of solvent A is not particularly limited, and its main function is to provide a liquid environment. The amount of acid-binding agent is 1.1-1.5 times the molar content of diphenylphosphine chloride, preferably 1.2 times.
[0062] In some preferred embodiments of the present invention, after obtaining solution A and solution B, solution B is preferably added dropwise to solution A, and then reacted at 0~10°C for 0.5~72 h, and then the temperature is raised to 30~70°C for another 0.5~72 h.
[0063] In this invention, after the reaction of solution A and solution B is completed, filtration is required to remove the hydrochloride formed by the acid-binding agent, and then solvent A is removed by rotary evaporation to obtain the first intermediate.
[0064] After obtaining the first intermediate, according to the present invention, the first intermediate, a silicon source, and an acid-binding agent are reacted to obtain a second intermediate. In this reaction, a diol containing a diphenylphosphinate structure undergoes a polycondensation reaction with silicon chloride to generate a chlorine-containing second intermediate.
[0065] In some embodiments of the present invention, it is preferable to treat the first intermediate as follows before proceeding with the reaction. The treatment process is as follows:
[0066] The first intermediate was mixed with solvent B, washed, and then subjected to rotary evaporation and drying to obtain a viscous liquid.
[0067] Solvent B is selected from dichloromethane and / or chloroform; the washing is performed using a saturated sodium bicarbonate aqueous solution and water, and the washing is repeated 2-3 times; the drying is preferably vacuum drying. The vacuum drying temperature is 70-90℃, preferably 80℃; the time is 10-20 h, preferably 12 h.
[0068] The purpose of the above treatment is to remove residual water and other organic solvents.
[0069] In some embodiments of the present invention, it is preferred to mix the silicon source, the acid-binding agent, and solvent A to obtain a mixed solution C; mix the viscous liquid with solvent A to obtain a mixed solution D; react the mixed solutions C and D at 0-10°C for 0.5-72 h, and then raise the temperature to 30-70°C for another 0.5-72 h, preferably at 0°C (ice-water bath conditions) for 1-24 h, and then raise the temperature to 50°C for another 3-48 h. More preferably, the mixed solution D is added dropwise to the mixed solution C for reaction, and after the reaction is complete, a second intermediate is obtained. In the present invention, the molar ratio of diphenylphosphine chloride to silicon source is 1:(1-2.5), preferably 1:(1.8-2.2), and more preferably 1:2. The amount of solvent A is not particularly limited, mainly serving to provide a liquid environment, and the amount of acid-binding agent is 1.1-1.5 times the molar content of silicon source, preferably 1.2 times.
[0070] Finally, the second intermediate is reacted with the diol shown in Formula B to obtain the flame-retardant polyol shown in Formula I. In this reaction step, the Si-Cl bond of the second intermediate undergoes a polycondensation reaction with the hydroxyl group of the diol to prepare the long-chain flame-retardant polyol. In this invention, the molar ratio of the diphenylphosphine chloride to the diol shown in Formula B is 1:(1~4), preferably 1:(2~3).
[0071] In some embodiments of the present invention, the diol shown in Formula B is preferably reacted with the second intermediate at 30-70°C for 0.5-72 h, preferably at 40-60°C for 2-48 h, according to the amount used. After the reaction is completed, filtration is preferably required to remove the hydrochloride formed by the acid-binding agent in the previous step, and then solvent A is removed by rotary evaporation to obtain the crude product.
[0072] In a preferred embodiment of the present invention, the crude product is preferably mixed with solvent B, washed, and then subjected to rotary evaporation and drying to obtain a flame-retardant polyol. This removes the hydrochloride salt formed by the acid-binding agent that was not filtered out during the reaction, thereby reducing the acid value of the flame-retardant polyol.
[0073] Solvent B is selected from dichloromethane and / or chloroform; the washing is performed using a saturated sodium bicarbonate aqueous solution and water, and the washing is repeated 2-3 times; the drying is preferably vacuum drying. The vacuum drying temperature is 70-90℃, preferably 80℃; the time is 10-20 h, preferably 12 h.
[0074] The preparation method of the flame-retardant polyol provided by the present invention is simple, convenient, easy to implement, and conducive to large-scale or industrial production.
[0075] The present invention also provides a polyurethane foam material, comprising component A: isocyanate, and component B: polyol. The polyol includes polyether polyol and the flame-retardant polyol described in the above-mentioned technical solutions. In the present invention, based on 100 parts by weight of the polyether polyol, the flame-retardant polyol is 10-20 parts by weight, preferably 15-18 parts.
[0076] In some specific embodiments of the present invention, flame-retardant polyol, polyether polyol 330 and A33, dibutyltin disilicate, silicone oil and water are preferably stirred evenly together, and then isocyanate (TDI) is added and stirred quickly and evenly. When the mixture begins to turn white, it is poured into a mold, pre-foamed for 15 min, and then placed in an 80°C oven for 24 h to obtain flame-retardant FPUF.
[0077] The prepared FPUF material, after testing, exhibits excellent flame retardant properties. When 10% (by weight) of P-Si-OH polyether polyol is added, it passes the vertical burning Cal TB117 test and continues to pass the test after a 22-hour heat aging test at 140 °C. Its tensile strength increases from 145 kPa to 214 kPa, and its elongation at break increases from 132% to 186%. After 100 cycles of compression, its strength recovery rate and deformation recovery rate remain essentially consistent with pure FPUF. The compression set at 70 °C and 50% permanent compression set is only 4.9%. These results demonstrate that the flame-retardant FPUF material provided by this invention possesses excellent flame retardancy and mechanical properties.
[0078] The above results indicate that the flame-retardant polyols provided by this invention can endow FPUF with excellent high flame retardancy, high fire safety, and mechanical properties.
[0079] To further illustrate the present invention, the following embodiments provide a detailed description. The experimental materials used in the following embodiments of the present invention are all commercially available products.
[0080] The performance testing methods involved are as follows:
[0081] Density was calculated from the volume and weight of the flexible polyurethane foam according to ISO 845:2006; vertical burning was tested according to Cal TB 117 standard, with a sample size of 30.48 cm × 7.62 cm × 1.27 cm; limiting oxygen index was tested according to GB / T 2406.2-2009, with a sample size of 10 mm × 10 mm × 150 mm.
[0082] The tensile properties of FPUF were tested according to ISO 1798:2008. A universal testing machine was used, with a 500N test element and a tensile speed of 500 mm / min. Compression cycling was performed with a 500N test element, at 50% compression set and 20 mm / min. -1 Tested at compression rate. Permanent compression rebound tests were performed on FPUF samples measuring 50 mm × 50 mm × 25 mm according to ISO 1856-2000. The samples were held at 70°C for 22 h, with a compression deformation of 50%.
[0083] Example 1
[0084] Preparation of P-Si-OH flame-retardant polyols:
[0085] In a three-necked flask, 0.2 mol (18.4 g) of glycerol was dispersed in 100 mL of anhydrous tetrahydrofuran, and 0.21 mol (21.2 g) of triethylamine was added. 0.2 mol (47.3 g) of diphenylphosphine chloride was dissolved in 100 mL of tetrahydrofuran. The solutions were added dropwise to the three-necked flask through a dropping funnel under a nitrogen atmosphere and in an ice-water bath at 0 °C. The mixture was stirred for 1 h, then heated to 50 °C and reacted for 3 h. Triethylamine hydrochloride was removed by filtration, and tetrahydrofuran was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and excess triethylamine hydrochloride was removed by repeated extraction with 50 mL of saturated NaHCO3 aqueous solution and deionized water. Dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 80 °C for 12 h to obtain a viscous liquid a.
[0086] Under ice bath conditions, 0.4 mol (51.6 g) of dichlorodimethylsilane, 0.9 mol (91.1 g) of triethylamine, and anhydrous tetrahydrofuran were added to a three-necked flask. 0.2 mol (58.6 g) of a dissolved in 100 mL of anhydrous tetrahydrofuran was added dropwise to the flask. The reaction was carried out in an ice bath for 1 h, then heated to 50 °C for 3 h. 0.21 mol of 1,4-butanediol (19.1 g) was added dropwise through a dropping funnel and reacted for 5 h. Triethylamine hydrochloride was removed by filtration, and tetrahydrofuran was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and excess triethylamine hydrochloride was removed by repeated extraction with 50 mL of saturated NaHCO3 aqueous solution and deionized water. Dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 80 °C for 12 h to obtain a viscous liquid polyol P-Si-OH. 31 PNMR and 1 H NMR spectrum as shown Figure 1 and Figure 2 As shown. Flight mass spectrometry analysis determined it to be a mixture, with the main component having a molecular weight of 1075.92 and a degree of polymerization (n) of 2. Its structural formula is as follows:
[0087] ;
[0088] Polyol P-Si-OH.
[0089] The obtained polyol P-Si-OH was mixed with polyether polyol 330, A33, dibutyltin disilicate, silicone oil, and water until homogeneous. Then, TDI was added, and the mixture was quickly stirred until homogeneous. The mixture was then poured into a mold and pre-foamed at room temperature for 15 min. Finally, it was placed in an oven at 80℃ for 24 h to prepare polyurethane foam material. The specific formulation and performance data are shown in Table 1.
[0090] Example 2
[0091] Polyol P-Si-OH was prepared according to Example 1, and polyurethane foam material was prepared according to the method of Example 1, the only difference being that the mass of polyol P-Si-OH added was 15% of the mass of polyether polyol. Specific formulations and performance data are shown in Table 1.
[0092] Example 3
[0093] Preparation of P-Si-OH-1 flame-retardant polyol:
[0094] In a three-necked flask, 0.2 mol (26.8 g) of trimethylolpropane was dispersed in 100 mL of anhydrous N,N-dimethylformamide, and 0.21 mol (16.6 g) of pyridine was added. 0.2 mol (47.3 g) of diphenylphosphine chloride was dissolved in 100 mL of N,N-dimethylformamide. The solutions were added dropwise to the three-necked flask through a dropping funnel under a nitrogen atmosphere and in an ice-water bath at 0 °C. After stirring for 1 h, the temperature was raised to 70 °C and reacted for 3 h. The pyridine hydrochloride was removed by filtration, and the N,N-dimethylformamide was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and then repeatedly extracted with 50 mL of saturated NaHCO3 aqueous solution and deionized water to remove excess pyridine hydrochloride. The dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 80 °C for 12 h to obtain a viscous liquid a.
[0095] Under ice bath conditions, 0.4 mol (51.6 g) of dichlorodimethylsilane, 0.9 mol (71.2 g) of pyridine, and anhydrous N,N-dimethylformamide were added to a three-necked flask. 0.2 mol (61.3 g) of a dissolved in 100 mL of anhydrous N,N-dimethylformamide was added dropwise to the flask. The reaction was carried out in an ice bath for 1 h, then heated to 50 °C and reacted for another 3 h. 0.21 mol (13.0 g) of ethylene glycol dissolved in 150 mL of N,N-dimethylformamide was then added and reacted for 5 h. The pyridine hydrochloride was removed by filtration, and the N,N-dimethylformamide was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and then repeatedly extracted with 50 mL of saturated NaHCO3 aqueous solution and deionized water to remove excess pyridine hydrochloride. Dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 100 °C for 12 h to obtain a viscous liquid polyol P-Si-OH-1 with a degree of polymerization n of 2~4. The structural formula is as follows:
[0096]
[0097] polyol P-Si-OH-1
[0098] The obtained polyol P-Si-OH-1 was mixed with polyether polyol 330, A33, dibutyltin disilicate, silicone oil, and water until homogeneous. Then, TDI was added, and the mixture was quickly stirred until homogeneous. The mixture was then poured into a mold and pre-foamed at room temperature for 15 min. Finally, it was placed in an oven at 80℃ for 24 h to prepare polyurethane foam material. The specific formulation and performance data are shown in Table 1.
[0099] Example 4
[0100] Polyol P-Si-OH-1 was prepared according to Example 3, and polyurethane foam material was prepared according to the method of Example 1, the only difference being that the mass of polyol P-Si-OH-1 added was 15% of the mass of polyether polyol. Specific formulations and performance data are shown in Table 1.
[0101] Example 5
[0102] Preparation of P-Si-OH-2 flame-retardant polyols:
[0103] In a three-necked flask, 0.2 mol (21.2 g) of 1,2,4-butanetriol was dispersed in 100 mL of anhydrous N,N-dimethylformamide, and 0.21 mol (16.6 g) of pyridine was added. 0.2 mol (47.3 g) of diphenylphosphine chloride was dissolved in 100 mL of N,N-dimethylformamide. The solutions were added dropwise to the three-necked flask through a dropping funnel under a nitrogen atmosphere and in an ice-water bath at 0 °C. After stirring for 1 h, the temperature was raised to 70 °C and reacted for 3 h. The pyridine hydrochloride was removed by filtration, and the N,N-dimethylformamide was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and then repeatedly extracted with 50 mL of saturated NaHCO3 aqueous solution and deionized water to remove excess pyridine hydrochloride. The dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 100 °C for 12 h to obtain a viscous liquid a.
[0104] 0.4 mol (51.6 g) of dichlorodimethylsilane, 0.9 mol (71.2 g) of pyridine, and anhydrous N,N-dimethylformamide were added to a three-necked flask under ice bath conditions. 0.2 mol (61.3 g) of a dissolved in 100 mL of anhydrous N,N-dimethylformamide was added dropwise to the flask. The reaction was carried out in an ice bath for 1 h, then heated to 50 °C for 3 h. 0.21 mol (13.0 g) of ethylene glycol dissolved in 150 mL of N,N-dimethylformamide was added through a dropping funnel and reacted for 5 h. Pyridine hydrochloride was removed by filtration, and N,N-dimethylformamide was removed by rotary evaporation. The crude product was dissolved in 100 mL of dichloromethane, and then repeatedly extracted with 50 mL of saturated NaHCO3 aqueous solution and deionized water to remove excess pyridine hydrochloride. Dichloromethane was removed by rotary evaporation, and the product was dried under vacuum at 100 °C for 12 h to obtain a viscous liquid polyol P-Si-OH-2 with a degree of polymerization n of 2-3. The structural formula is as follows:
[0105] Flame-retardant polyol P-Si-OH-2
[0106] Comparative Example 1
[0107] Preparation of pure FPUF
[0108] Polyether polyol 330 was mixed with A33, dibutyltin disilicate, silicone oil, and water until homogeneous. Then, TDI was added and the mixture was stirred rapidly until homogeneous. When the mixture began to turn white, it was poured into a mold and pre-foamed for 15 minutes. Finally, it was placed in an 80°C oven and cured for 24 hours to obtain the polyurethane foam material. Specific formulation and performance data are shown in Table 1.
[0109] Comparative Example 2
[0110] Preparation of Dimethyl Methyl Phosphate Flame Retardant FPUF
[0111] Dimethyl methyl phosphate was added to polyether polyol 330 at 10% of its mass in the polyurethane foam formulation. The mixture was stirred for 10 min, and then stirred thoroughly with A33, dibutyltin disilicate, silicone oil, and water. TDI was then added and stirred rapidly until the mixture began to turn white. The mixture was then poured into a mold and pre-foamed for 15 min. Finally, it was placed in an 80℃ oven and cured for 24 h to obtain the polyurethane foam material. Specific formulation and performance data are shown in Table 1.
[0112] Table 1
[0113] Group Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Polyether polyols (g) 100 100 100 100 100 100 100 Flame-retardant polyols (g) 10 15 10 15 10 0 0 DMMP(g) 0 0 0 0 0 0 10 <![CDATA[H2O(g)]]> 3 3 3 3 3 3 3 A33(g) 0.05 0.04 0.04 0.04 0.04 0.1 0.1 Dibutyltin silicate (g) 0.04 0.04 0.04 0.04 0.04 0.05 0.05 Silicone oil (g) 1.5 1.5 1.5 2.0 1.5 0.5 2.0 TDI 80 / 20 (g) 43 44 43 44 43 41 41 <![CDATA[Density (kg / m 3 )]]> 32.9 33.4 33.1 34.5 33.1 30.6 32.5 LOI (%) 21.6±0.2 22.3±0.2 21.9±0.2 22.6±0.2 21.7±0.2 18.5±0.2 21.6±0.2 Cal TB 117 test pass pass pass pass pass Not passed pass LOI (%) after 22 h thermal aging test 21.6±0.2 22.3±0.2 21.9±0.2 22.6±0.2 21.7±0.2 18.5±0.2 19.6±0.2 Cal TB 117 test after 22 h thermal aging test pass pass pass pass pass Not passed Not passed
[0114] As shown in Table 1, adding only 10% of the flame-retardant polyol by mass of the polyether polyol is sufficient to make the prepared FPUF pass the Cal TB 117 test. Furthermore, since the flame-retardant polyol provided by this invention can participate in the foaming and curing process of the FPUF, its LOI and Cal TB 117 test results after thermal aging remain consistent with those before aging.
[0115] The mechanical property data of the flame-retardant FPUF materials obtained in Examples 1-5 and Comparative Examples 1-2 are shown in Table 2 below:
[0116] Table 2
[0117]
[0118] As shown in Table 2, the presence of silicon-oxygen bonds in the flame-retardant polyol provided by the present invention can increase the flexibility of the molecular chain in FPUF, and the phosphorus-oxygen bonds in P-Si-OH can form hydrogen bonds with urethane, thereby endowing FPUF with high tensile properties and good compression and resilience properties.
[0119] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A flame-retardant polyol of Formula I: Formula I; in, R1 is selected from hydrogen, substituted or unsubstituted C1-C6 alkyl groups, and R2 is selected from -(CH2). m -, m can be any integer from 2 to 6; n can be any integer from 1 to 4.
2. The flame-retardant polyol according to claim 1, characterized in that, R1 is selected from hydrogen, substituted or unsubstituted C1-C3 alkyl groups; The value of m is 2 or 3.
3. The flame-retardant polyol according to claim 1 or 2, characterized in that, The flame-retardant polyol is selected from any one of the following formulas: 。 4. A method for preparing a flame-retardant polyol as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1: Reaction of diphenylphosphine chloride with an acid-binding agent and a mixture of triols represented by formula A yields the first intermediate; S2: React the first intermediate, silicon source, and acid-binding agent to obtain the second intermediate; S3: React the second intermediate with the diol shown in Formula B to obtain the flame-retardant polyol shown in Formula I; Formula A; Formula B; Wherein, R1 is selected from hydrogen, substituted or unsubstituted C1-C6 alkyl groups, and R2 is selected from -(CH2). m -, m can be any integer from 2 to 6.
5. The preparation method according to claim 4, characterized in that, The molar ratio of the diphenylphosphinochloride, the triol represented by formula A, the silicon source, and the diol represented by formula B is 1:(1~1.5):(1~2.5):(1~4).
6. The preparation method according to claim 4 or 5, characterized in that, The acid-binding agent in step S1 or step S2 is selected from any one or more of triethylamine, pyridine / or imidazole; The silicon source is selected from dichlorodimethylsilane; The reaction in step S1 is carried out in the presence of a solvent selected from one or more of tetrahydrofuran, chloroform, acetonitrile, dichloromethane, N,N-dimethylformamide, or dimethylacetamide.
7. The preparation method according to any one of claims 4 to 6, characterized in that, After the reaction described in step S1 is carried out at 0~10℃ for 0.5~72 h, the temperature is raised to 30~70℃ and the reaction is carried out for another 0.5~72 h. After the reaction described in step S2 is carried out at 0~10℃ for 0.5~72 h, the temperature is raised to 30~70℃ and the reaction is carried out for another 0.5~72 h. The reaction temperature in step S3 is 30~70℃, and the reaction time is 0.5~72 h; The reactions in steps S1, S2, and S3 are all carried out under an inert atmosphere.
8. The preparation method according to any one of claims 4 to 7, characterized in that, The first intermediate in step S2 undergoes the following processing: The first intermediate was mixed with a solvent, washed, and then subjected to rotary evaporation and drying to obtain a viscous liquid. The solvent is selected from dichloromethane and / or chloroform.
9. A polyurethane foam material, characterized in that, Including isocyanates and polyols; The polyol includes polyether polyol and flame-retardant polyol according to any one of claims 1 to 3 or flame-retardant polyol prepared by any one of claims 4 to 8.
10. The polyurethane foam material according to claim 9, characterized in that, Based on 100 parts by weight of the polyether polyol, the flame-retardant polyol is 10 to 20 parts by weight.