Bio-based phosphorus-containing polyol as well as preparation method and application thereof

Abstract

The invention relates to bio-based phosphorus-containing polyol as well as a preparation method and application thereof, and belongs to the field of polyol materials. The invention aims to solve the technical problems that the traditional polyurethane material additive flame retardant is low in flame retardant efficiency and easy to migrate, so that the mechanical property is reduced, and the raw materials are non-renewable. The preparation method comprises the following steps: carrying out condensation reaction on phytic acid and urea to prepare ammonium phytate, reacting the ammonium phytate with a compound containing a plurality of active groups in a specific organic solvent, and adjusting the mass ratio and temperature conditions to prepare the phosphorus-containing polyol. Two or more thermally stable phosphorus groups and ammonium groups are introduced into the structure of the polyol, so that the polyol has dual flame-retardant effects and charge conduction characteristics. The flame-retardant antistatic agent is embedded into a polyurethane matrix for continuous reaction forming and has a synergistic effect with the antistatic agent, and the flame-retardant antistatic material is obtained. According to the technical scheme, a bio-based-phosphorus synergistic flame-retardant network and an ionic conduction channel are constructed, compared with a traditional process, energy consumption is reduced, and the product has excellent flame retardance and mechanical property.

Description

Technical Field

[0001] The present invention belongs to the field of polyol materials, and relates to a bio-based phosphorus-containing polyol, a preparation method thereof, and an application thereof. Background Art

[0002] Polyurethane (PU) is a block copolymer with repeating urethane (-NHCOO-) groups in its molecular chain. PU not only has good impact resistance, chemical resistance, and low-temperature resistance, but also has excellent flexibility and viscoelasticity, and is widely used in light industry, electronics, automobiles, national defense and other fields. However, PU is flammable, which limits its application in some special fields (such as aviation and electronic and electrical equipment). Traditional flame retardants (such as halogen-based, inorganic phosphorus-based, etc.) have problems such as high toxicity, strong migration, or poor compatibility with the matrix. Bio-based polyols are regarded as ideal precursors for environmentally friendly flame retardant materials due to their renewable nature, low toxicity, and functionalizable modification. With the increasingly strict environmental protection regulations and the growing demand for sustainable development, bio-based flame retardant materials have become a research hotspot in the polymer field.

[0003] In the prior art, the flame retardant modification of bio-based polyols still faces many key bottlenecks. Currently, common bio-based polyols (such as castor oil-based, lignin-based) have hydroxyl functional groups, but their molecular structures lack flame retardant elements (such as phosphorus, nitrogen). When directly applied to materials such as polyurethane, 10%-30% of flame retardant fillers (such as ammonium polyphosphate APP) need to be added additionally, resulting in a significant decline in the mechanical properties of the materials. Existing phosphorus modification technologies are mainly divided into physical blending method and chemical bonding method. In the physical blending method, phosphorus elements are prone to migration, resulting in a decrease in flame retardant efficiency. The chemical bonding method mainly reacts through P-Cl bonds with hydroxyl groups, usually requiring strong acid catalysts. The by-product HCl will corrode equipment, and the phosphorus content of the product is usually low, and the flame retardant efficiency is limited. Summary of the Invention

[0004] In view of this, the present invention develops a new type of bio-based phosphorus-containing polyol. Through in-situ phosphorus embedding structure, chemical bonding phosphorus (instead of physical doping) of the bio-based molecular skeleton is realized, so that the phosphorus content is controllable and there is no migration; a multi-functional synergistic effect is utilized, and the phosphorus-nitrogen structure is used to synergistically improve the flame retardant efficiency and inhibit dripping. One of the purposes of the present invention is to provide a bio-based phosphorus-containing polyol, the second purpose is to provide a preparation method of a bio-based phosphorus-containing polyol, and the third purpose is to provide an application of a bio-based phosphorus-containing polyol.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a bio-based phosphorus-containing polyol, and the bio-based phosphorus-containing polyol is a compound of structural formula I, and the structural formula I is: Wherein R1~R 12contains compounds of Structural Formula II in a number ≥ 2, and Structural Formula II is: HO(CH2) n - any one of them, where n is an integer ≥ 2, and the remaining group is: NH4 + ;

[0007] Furthermore, the present invention provides a preparation method of the bio-based phosphorus-containing polyol, and the steps are as follows:

[0008] (1) Add phytic acid and urea into a reaction kettle, dissolve them in water, heat to 60 - 150 °C for condensation reflux reaction for 20 - 200 min, purify with a solvent and dry to obtain ammonium phytate;

[0009] (2) Add the compound of Structural Formula III any one of aliphatic polyols and polyphenol hydroxyl groups into a flask, add an organic solvent, heat to 30 °C - 100 °C to dissolve, and at 25 °C - 150 °C, add the ammonium phytate obtained in step (1) and react for 1 h - 10 h. After removing the solvent and drying, the bio-based phosphorus-containing polyol can be obtained;

[0010] Preferably, in step (1), the molar ratio of phytic acid to urea is 1:1 - 7;

[0011] Preferably, in step (2), the organic solvent is any one or several of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene, dichlorobenzene, trichlorobenzene, ethylene glycol methyl ether, ethylene glycol ethyl ether or 1,4-dioxane;

[0012] Preferably, in step (2), the molar ratio of the compound of Structural Formula III to ammonium phytate is 2 - 5:1;

[0013] Preferably, in step (2), the drying process is specifically: drying at a temperature of 90 °C - 180 °C and a negative pressure of 0.01 - 0.1 MPa;

[0014] Furthermore, the present invention provides an application of the bio-based phosphorus-containing polyol in the preparation of flame-retardant and antistatic polyurethane materials;

[0015] Furthermore, the present invention provides a flame-retardant and antistatic polyurethane material;

[0016] Preferably, the preparation method of the flame-retardant and antistatic polyurethane material is as follows:

[0017] (1) Mix the antistatic agent with the bio-based phosphorus-containing polyol, pass through a water removal device and then mix with 4,4`-diphenylmethane diisocyanate to obtain a resin mixture,

[0018] (2) Preheat the glass fiber to 100 - 150 °C and then draw it into the impregnation mold. Inject the resin mixture from step (1) into the impregnation mold, and then maintain the temperature inside the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile.

[0019] (3) Draw the obtained rough profile into the forming mold, maintain the temperature inside the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane profile.

[0020] Preferably, the mass ratio of the antistatic agent to the bio-based phosphorus-containing polyol is 1:0.5 - 5.

[0021] The beneficial effects of the present invention are as follows:

[0022] The bio-based phosphorus-containing polyol of the present invention can be used for the flame retardancy of thermosetting resins such as epoxy resins and polyurethanes. It has high flame retardancy (efficient flame retardancy UL-94v0 can be achieved by adding 8%), can self-crosslink and expand into carbon, and crosslink with pyrolysis small molecules of polymer materials at high temperature to generate a carbon layer with high thermal stability.

[0023] The bio-based phosphorus-containing polyol of the present invention realizes controllable phosphorus content by in-situ phosphorus embedding structure, bonding phosphorus in the chemical bond of the bio-based molecular skeleton (instead of physical doping), can react with isocyanates, etc. to obtain functional flame-retardant thermosetting resins, belongs to intrinsic flame retardancy, and has a multi-functional synergistic effect. It uses the synergistic effect of the phosphorus-nitrogen structure to improve the flame retardancy efficiency and has the advantage of preventing the precipitation of flame retardants. Specifically, it is reflected in the following aspects:

[0024] 1. Significantly improved flame retardancy: Through the thermal decomposition of the bio-based phosphorus-containing polyol, phosphate ester substances are generated to promote the formation of a dense carbon layer, and at the same time, non-combustible gases such as NH3 are released to achieve gas-solid two-phase synergistic flame retardancy. The flaming combustion time of the examples (1.4 - 2.4 s) is reduced by more than 90% compared with the comparative examples (32 - 42.3 s), and the non-flaming combustion time (1.1 - 2.9 s) is shortened by 60% - 85% compared with the comparative examples (7.5 - 19.6 s).

[0025] 2. Enhanced mechanical properties: The bio-based polyol is embedded in the polyurethane main chain through chemical bonding, avoiding phase separation and strengthening the crosslinked structure. The tensile strength of the examples reaches 1272 - 1385 MPa (3% - 8% higher than that of the comparative examples), and the bending strength is up to 1421 MPa at most (5.7% - 18.3% higher than that of the comparative examples).

[0026] 3. Optimized antistatic performance: Through the charge conduction of NH4 + ions in the polyol and the synergistic effect of the antistatic agent, the surface resistance of the examples is increased to 3.8×10 9 -4.7×10 9Ω, compared with the comparative example (1.2×10 9 -2.5×10 9 Ω), it is increased by 1.5 - 3.9 times, effectively achieving static charge dissipation.

[0027] Other advantages, objectives and features of the present invention will, to some extent, be elaborated in the subsequent specification, and to some extent, will be obvious to those skilled in the art based on the study of the following text, or can be learned from the practice of the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the following specification. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be described in detail preferably with reference to the accompanying drawings, where:

[0029] Figure 1 is the 1H NMR spectrum of PA-A;

[0030] Figure 2 is the 1H NMR spectrum of PA-B. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The following specific examples illustrate the embodiments of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the diagrams provided in the following examples only illustrate the basic concept of the present invention in a schematic manner. Without conflict, the following examples and the features in the examples can be combined with each other.

[0032] Among them, the accompanying drawings are only for illustrative purposes, showing only schematic diagrams, not physical diagrams, and should not be construed as a limitation to the present invention; for better illustrating the embodiments of the present invention, some components in the accompanying drawings will be omitted, enlarged or reduced, and do not represent the dimensions of the actual product; for those skilled in the art, it is understandable that some well-known structures and their descriptions in the accompanying drawings may be omitted.

[0033] In the accompanying drawings of the embodiments of the present invention, the same or similar reference numerals correspond to the same or similar components; in the description of the present invention, it should be understood that if there are terms such as "upper", "lower", "left", "right", "front", "rear", etc. indicating the orientation or positional relationship, they are based on the orientation or positional relationship shown in the accompanying drawings. This is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, the terms describing the positional relationship in the accompanying drawings are only for illustrative purposes and cannot be construed as a limitation of the present invention. For those of ordinary skill in the art, the specific meanings of the above terms can be understood according to specific circumstances.

[0034] Example 1

[0035] A bio-based phosphorus-containing polyol, and the specific preparation method is as follows:

[0036] (1) Add 66 g of phytic acid and 12 g of urea 60 to a reaction kettle, dissolve in water, heat to 100 °C, carry out condensation reflux reaction for 60 min, purify with anhydrous ethanol solvent and carry out freeze-drying for 24 h to obtain ammonium phytate;

[0037] (2) Add the compound of structural formula III (0.1 mol) to a flask equipped with a condensation device, add acetone, heat to 60 °C to dissolve, and at 100 °C, add ammonium phytate and the compound of structural formula III (where the molar ratio of the compound of structural formula III to ammonium phytate is 2:1), react for 5 h, remove the solvent, and after drying, obtain the bio-based phosphorus-containing polyol PA-A;

[0038] The compound of the above structural formula III is ethylene glycol.

[0039] The structural formula of the prepared PA-A is as follows:

[0040] PA-A:

[0041]

[0042] Example 2

[0043] A bio-based phosphorus-containing polyol, and the specific preparation method is as follows:

[0044] (1) Add 66 g of phytic acid and 12 g of urea 60 to a reaction kettle, dissolve in water, heat to 100 °C, carry out condensation reflux reaction for 60 min, purify with anhydrous ethanol solvent and carry out freeze-drying for 24 h to obtain ammonium phytate;

[0045] (2) Add the compound of Structural Formula III (0.1 mol) to a flask equipped with a condensation device. After adding acetone, heat it up to 60 °C to dissolve. At 100 °C, add ammonium phytate and the compound of Structural Formula III (where the molar ratio of the compound of Structural Formula III to ammonium phytate is 2:1), react for 5 h, then remove the solvent. After drying, the bio-based phosphorus-containing polyol PA-B can be obtained:

[0046] The DP of the above compound of Structural Formula III is

[0047] The structural formula of the prepared PA-B is as follows:

[0048]

[0049] Example 3

[0050] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0051] (1) Mix 1.5 g of antistatic agent and 0.5 g of PA-B into 11.75 g of polyether polyol. After passing through a water removal device, mix it with 11.25 g of 4,4`-diphenylmethane diisocyanate (MDI) in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0052] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw the preheated 75 g of glass fiber into an impregnation mold. Inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C and react for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0053] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain the profile flame-retardant and antistatic polyurethane (UP7).

[0054] Example 4

[0055] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0056] (1) Mix 1.5 g of antistatic agent and 1 g of PA-B into 11.5 g of polyether polyol. After passing through a water removal device, mix it with 11 g of 4,4`-diphenylmethane diisocyanate (MDI) in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0057] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C and react for 1 - 4 min to obtain a rough profile. Ordinary glass fiber felt can be optionally used on the surface of the profile.

[0058] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane profile (UP 8).

[0059] Example 5

[0060] A flame-retardant and antistatic polyurethane, the specific preparation method is as follows:

[0061] (1) Mix 1.5 g of antistatic agent and 1.5 g of PA-B into 11.25 g of polyether polyol, and after passing through a water removal device, mix it with 10.75 g of 4,4`-diphenylmethane diisocyanate (MDI) in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0062] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C and react for 1 - 4 min to obtain a rough profile. Ordinary glass fiber felt can be optionally used on the surface of the profile.

[0063] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane profile (UP 9).

[0064] Example 6

[0065] A flame-retardant and antistatic polyurethane, the specific preparation method is as follows:

[0066] (1) Mix 1.5 g of antistatic agent and 2 g of PA-B into 11 g of polyether polyol, and after passing through a water removal device, mix it with 10.5 g of 4,4`-diphenylmethane diisocyanate (MDI) in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0067] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold. Inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C and react for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0068] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min, and obtain a flame-retardant and antistatic polyurethane for profiles (UP 10).

[0069] Example 7

[0070] A flame-retardant and antistatic polyurethane, the specific preparation method is as follows:

[0071] (1) Mix 1.5 g of antistatic agent and 0.5 g of PA-A into 11.75 g of polyether polyol, and after passing through a water removal device, add it to 11.25 g of 4,4`-diphenylmethane diisocyanate (MDI) and mix in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0072] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold. Inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C and react for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0073] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min, and obtain a flame-retardant and antistatic polyurethane for profiles (UP 11).

[0074] Example 8

[0075] A flame-retardant and antistatic polyurethane, the specific preparation method is as follows:

[0076] (1) Mix 1.5 g of antistatic agent and 1 g of PA-A into 11.5 g of polyether polyol, and after passing through a water removal device, add it to 11 g of 4,4`-diphenylmethane diisocyanate (MDI) and mix in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0077] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0078] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane for profiles (UP 12).

[0079] Example 9

[0080] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0081] (1) Mix 1.5 g of antistatic agent and 1.5 g of PA-A into 11.25 g of polyether polyol, and after passing through a water removal device, mix it with 10.75 g of 4,4'-diphenylmethane diisocyanate (MDI) in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0082] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0083] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane for profiles (UP 13).

[0084] Example 10

[0085] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0086] (1) Mix 1.5 g of antistatic agent and 2 g of PA-A into 11 g of polyether polyol, and after passing through a water removal device, mix it with 10.5 g of 4,4'-diphenylmethane diisocyanate (MDI) in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0087] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold. Inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0088] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane (UP 14) profile.

[0089] The flame-retardant mechanism of the flame-retardant polyurethane material prepared from the bio-based phosphorus-containing polyol of the present invention is as follows:

[0090]

[0091] Comparative Example 1

[0092] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0093] (1) Add 1.5 g of an antistatic agent to 12 g of polyether polyol and mix well. After passing through a water removal device, add it to 11.5 g of 4,4`-diphenylmethane diisocyanate (MDI) and mix in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C);

[0094] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold. Inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0095] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane (UP1).

[0096] Comparative Example 2

[0097] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0098] (1) Add 2 g of bisphenol A-bis(diphenyl phosphate) (BDP) flame retardant and 1.5 g of an antistatic agent to 11 g of polyether polyol and mix well. After passing through a water removal device, add it to 10.5 g of 4,4`-diphenylmethane diisocyanate (MDI) and mix in a static mixing device. The above operations are all carried out at room temperature (25 ± 5 °C).

[0099] (2) Preheat the glass fiber to 100 - 150 °C using a preheating device, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture from the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber felt can be optionally used on the surface of the profile.

[0100] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame - retardant and antistatic polyurethane for profiles (UP2).

[0101] Comparative Example 3

[0102] A flame - retardant and antistatic polyurethane, the specific preparation method is as follows:

[0103] (1) Mix 2 g of the flame retardant tris(2 - chloroethyl) phosphate TCEP and 1.5 g of the antistatic agent into 11 g of polyether polyol, after passing through a water - removing device, add it to 10.5 g of 4,4` - diphenylmethane diisocyanate (MDI) and mix in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C).

[0104] (2) Preheat the glass fiber to 100 - 150 °C using a preheating device, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture from the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber felt can be optionally used on the surface of the profile.

[0105] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame - retardant and antistatic polyurethane for profiles (UP3).

[0106] Comparative Example 4

[0107] A flame - retardant and antistatic polyurethane, the specific preparation method is as follows:

[0108] (1) Mix 2 g of the flame retardant DP and 1.5 g of the antistatic agent into 11 g of polyether polyol, after passing through a water - removing device, add it to 10.5 g of 4,4` - diphenylmethane diisocyanate (MDI) and mix in a static mixing device to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C). DP:

[0109] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0110] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane for profiles (UP4).

[0111] Comparative Example 5

[0112] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0113] (1) Add 2 g of ammonium phytate and 1.5 g of antistatic agent to 11 g of polyether polyol, mix well, pass through a water removal device, and then add 10.5 g of 4,4`-diphenylmethane diisocyanate (MDI) to a static mixing device for mixing to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C).

[0114] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0115] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane for profiles (UP5).

[0116] Comparative Example 6

[0117] A flame-retardant and antistatic polyurethane, and the specific preparation method is as follows:

[0118] (1) Add 2 g of ethylene glycol and 1.5 g of antistatic agent to 11 g of polyether polyol, mix well, pass through a water removal device, and then add 10.5 g of 4,4`-diphenylmethane diisocyanate (MDI) to a static mixing device for mixing to obtain a resin mixture. The above operations are all carried out at room temperature (25 ± 5 °C).

[0119] (2) Use a preheating device to preheat the glass fiber to 100 - 150 °C, then draw 75 g of the preheated glass fiber into an impregnation mold, inject the resin mixture in the storage unit into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for 1 - 4 min to obtain a rough profile. Ordinary glass fiber mats can be optionally used on the surface of the profile.

[0120] (3) Use a traction device to draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane (UP6) profile.

[0121] Performance test of Example 11

[0122] Perform performance tests on the flame-retardant and antistatic polyurethanes prepared in the above examples and comparative examples. The results are shown in Table 1 below.

[0123] Measure the mechanical properties, flame-retardant properties, and antistatic properties of the flame-retardant and antistatic polyurethane composites obtained in Examples 3 - 10. Refer to Standard GB / T 3354 - 2014 to measure the tensile strength of the profile; refer to Standard GB / T 3356 - 2014 to measure the flexural strength and flexural modulus of the profile; refer to Standard MT113 - 1995 to measure the average time of 6 specimens for flaming combustion with an alcohol burner, the maximum time of a single specimen for flaming combustion with an alcohol burner, the total time of 6 specimens for non-flaming combustion with an alcohol burner, and the maximum time of a single specimen for non-flaming combustion with an alcohol burner; refer to MT113 - 1995 to measure the surface resistance of the flame-retardant and antistatic polyurethane composite. The measurement results are shown in Tables 1 and 2.

[0124] Table 1 Performance test results of the comparative examples

[0125]

[0126] Table 2 Performance test results of the examples

[0127]

[0128] From Tables 1 and 2, the excellent properties of the flame-retardant and antistatic polyurethane prepared from the bio-based phosphorus-containing polyol of the present invention are as follows:

[0129] 1. The flame-retardant performance is significantly improved

[0130] The bio-based phosphorus-containing polyol generates phosphate ester substances through the thermal decomposition of ammonium phytate, promotes the formation of a carbon layer, isolates oxygen and heat; at the same time, the ammonium group decomposes to release non-combustible gases (such as NH3), dilutes the combustible gases, and realizes gas-solid synergistic flame retardancy.

[0131] Flame combustion time: The average flame combustion time (1.4 - 2.4 seconds) of the examples (such as UP7 - UP14) is much lower than that of the comparative examples (for example, 42.3 seconds for Comparative Example 4 and 32 seconds for Comparative Example 5).

[0132] Smokeless combustion time: The smokeless combustion time of the examples (1.1 - 2.9 seconds) is also significantly better than that of the comparative examples (7.5 - 19.6 seconds).

[0133] 2. Enhanced mechanical properties

[0134] The bio - based polyol is embedded in the polyurethane main chain through chemical bonds, avoiding phase separation caused by traditional physically added flame retardants, maintaining the structural integrity of the material, and at the same time, the cross - linking of phosphorus groups enhances rigidity.

[0135] Tensile strength: The tensile strength of the examples reaches 1272 - 1385 MPa, which is higher than that of the comparative examples (1197 - 1312 MPa).

[0136] Flexural strength: The flexural strength of the examples reaches up to 1421 MPa (UP10), which is significantly better than that of the comparative examples (1201 - 1345 MPa).

[0137] 3. Optimization of antistatic performance

[0138] NH4 + ions in the polyol provide a charge conduction channel, and cooperate with the antistatic agent to form a conductive network, effectively dissipating static charges.

[0139] Surface resistance: The surface resistance of the examples is 3.8×10 9 ~4.7×10 9 Ω, which is higher than that of the comparative examples (1.2×10 9 ~2.5×10 9 Ω).

[0140] 4. Comparative analysis

[0141] Comparative Example 5 (directly adding ammonium phytate): The flame retardant effect is poor (flame combustion for 32 seconds), which proves that physical mixing cannot efficiently exert the phosphorus - nitrogen synergistic effect.

[0142] Comparative Example 2 (BDP flame retardant): Although the flame retardant effect is good (flame for 2.8 seconds), its mechanical strength (tensile 1259 MPa) is lower than that of the examples, indicating that traditional flame retardants damage mechanical properties.

[0143] Example 3 (UP7): It has the best comprehensive performance, the shortest combustion time (flame for 2.4 seconds) and high mechanical strength (tensile 1385 MPa), verifying the effectiveness of the bio - based - phosphorus network design.

[0144] Through the chemical bonding of isocyanate and bio-based phosphorus-containing polyol, the present invention constructs an intrinsically flame-retardant and antistatic integrated structure, solves the pain points of poor migration and large mechanical loss of traditional flame retardants, and provides an innovative solution for high-performance polyurethane materials.

[0145] 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. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the purpose and scope of the present technical solution, and they should all be covered within the scope of the claims of the present invention.

Claims

1. Biobased phosphorus-containing polyol, characterized in that: The bio-based phosphorus-containing polyol is a compound of Structural Formula I, and the Structural Formula I is as follows: wherein R1 to R 12 contains a compound of Structural Formula II with a number ≥ 2, and the Structural Formula II is as follows: Any one of them, n is an integer ≥ 2, and the remaining group is: NH4 + .

2. The preparation method of the bio-based phosphorus-containing polyol according to claim 1, wherein: (1) Add phytic acid and urea into a reaction kettle, dissolve them in water, heat to 60 - 150 °C for condensation reflux reaction for 20 - 200 min, purify with a solvent and dry to obtain ammonium phytate; (2) Add any one of the compounds of structural formula III as an aliphatic polyol or a polyhydric phenolic hydroxyl group into a flask, add an organic solvent and heat to 30 °C to 100 °C for dissolution, and at 25 °C to 150 °C, add the ammonium phytate in step (1) and react for 1 h to 10 h. After removing the solvent and drying, a bio-based phosphorus-containing polyol can be obtained.

3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of phytic acid to urea is 1:1 - 7.

4. The preparation method according to claim 2, wherein: In step (2), the organic solvent is any one or more of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, chlorobenzene, dichlorobenzene, trichlorobenzene, ethylene glycol methyl ether, ethylene glycol ethyl ether or 1,4-dioxane.

5. The preparation method according to claim 2, characterized in that: In step (2), the molar ratio of the compound of structural formula Ⅲ to ammonium phytate is 2 - 5:

1.

6. The preparation method according to claim 2, characterized in that: In step (2), the drying process is specifically: drying at a temperature of 90 °C - 180 °C and a negative pressure of 0.01 - 0.1 MPa.

7. The application of the bio-based phosphorus-containing polyol according to claim 1 in the preparation of a flame-retardant and antistatic polyurethane material.

8. A flame-retardant and antistatic polyurethane material, characterized in that, The preparation method of the flame-retardant and antistatic polyurethane material is as follows: (1) Mix the antistatic agent with the bio-based phosphorus-containing polyol according to claim 1, pass through a water removal device and then mix with 4,4`-diphenylmethane diisocyanate to obtain a resin mixture, (2) Preheat the glass fiber to 100 - 150 °C and then draw it into an impregnation mold, inject the resin mixture of step (1) into the impregnation mold, and then maintain the temperature in the impregnation mold at 150 - 220 °C for reaction for 1 - 4 min to obtain a rough profile, (3) Draw the obtained rough profile into a forming mold, maintain the temperature in the forming mold at 130 - 160 °C for 1 - 4 min to obtain a flame-retardant and antistatic polyurethane profile.

9. The flame-retardant and antistatic polyurethane material according to claim 8, wherein: The mass ratio of the antistatic agent to the bio-based phosphorus-containing polyol is 1:0.5 - 5.

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