Low-viscosity intumescent flame-retardant phosphorus-hybridized hyperbranched organosilicon polymer and preparation method thereof

Abstract

The invention discloses a low-viscosity intumescent flame-retardant phosphorus-hybridized hyperbranched organosilicon polymer and a preparation method thereof. The low-viscosity intumescent flame-retardant phosphorus-hybridized hyperbranched organosilicon polymer is prepared by carrying out controllable hydrolytic condensation on a phosphorus-modified silane monomer and a silane monomer under an acidic condition; the hyperbranched organosilicon polymer with a highly branched and non-completely regular three-dimensional network structure is formed; the hyperbranched organosilicon polymer takes Si-O-Si as a main chain structure, and a side chain is rich in phosphorus. The preparation method comprises the following steps: mixing a basic catalyst, a phosphorus source, a glycidyl ether group-containing silane coupling agent and a solvent, reacting at 30-150 DEG C, and purifying to obtain a phosphorus-modified silane monomer; and mixing an acidic catalyst, water, a solvent, a silane monomer and a phosphorus-modified silane monomer, reacting at 60-100 DEG C, and purifying. The invention provides an efficient, environment-friendly and multifunctional innovative solution for high-end flame-retardant materials.

Description

Technical Field

[0001] The present invention belongs to silicone polymers and their preparation methods, and specifically relates to a low-viscosity expandable flame-retardant phosphorus-hybrid hyperbranched silicone polymer and a preparation method thereof. Background Art

[0002] With the rapid development of new energy vehicles, aerospace, and the construction industry, the flame-retardant requirements of polymer materials in extreme environments are becoming increasingly stringent. For example, in the field of new energy batteries, under the development trend of lightweight and high energy density of power battery modules, polymer materials used for the encapsulation of new energy batteries need to simultaneously meet the harsh flame-retardant requirements of UL94 V-0 level flame retardancy and heat runaway shock resistance. In the aerospace field, when aircraft re-enter the atmosphere, they face high-speed heat flux and dynamic oxygen erosion, requiring polymer materials to have the ability of low ablation rate, high char yield, and thermal oxidation resistance. In the field of super high-rise buildings, polymer materials used in construction are required to have UL94 V-0 level flame retardancy, and at the same time, they need to meet the requirements of low smoke density, low smoke release, and high mechanical properties.

[0003] To address the above problems, existing polymer materials usually improve the flame-retardant performance of the materials by adding flame retardants additionally. Among them, phosphorus-containing flame retardants have become the mainstream solution due to their high efficiency in forming carbon and free radical quenching effects. However, there are still the following key problems in their application in the above extreme environment flame retardancy. Specifically, traditional phosphorus-based flame retardants generally have the defects of insufficient thermal stability, easy moisture absorption, high migration rate, and deterioration of the mechanical properties of polymer materials. At the same time, in use, soluble phosphorus compounds in phosphorus-based flame retardants migrate into the environment, resulting in eutrophication of water bodies, and the potential poisoning hazards caused by the easy release of a large amount of toxic gases such as PH3 and P2O5 during combustion also pose safety risks to the environment and personnel, further restricting the use of phosphorus-based flame retardants in new energy vehicles and super high-rise building materials. In addition, traditional phosphorus-based flame retardants have poor adaptability to extreme conditions. Under high-speed heat flux or high oxygen concentration, a single phosphorus-based flame retardant mechanism is difficult to maintain the integrity of the carbon layer, resulting in heat protection failure, which also limits their application prospects in the aerospace field. Therefore, although traditional phosphorus-containing flame retardants can improve the basic flame-retardant performance of polymers, their defects in thermal stability, environmental friendliness, and extreme environment adaptability make it difficult to meet the stringent requirements of new energy batteries, aerospace and other fields for high-performance, high-temperature resistant, low-smoke and low-toxic materials. Developing a new flame-retardant system with high efficiency in flame retardancy, environmental friendliness, and extreme condition adaptability has become an urgent need in the industry and an urgent need to break through the industry bottleneck.

[0004] The silicon-phosphorus synergistic flame retardant has a dual flame retardant mechanism through the synergistic effect of silicon and phosphorus elements: a dense Si-O-P-C composite ceramic carbon layer is formed in the condensed phase, significantly improving the high-temperature ablation resistance of the material. In the gas phase, through free radical quenching reactions and the efficient adsorption of smoke by silicon-based particles, the flame retardant performance of the material is improved, and the smoke density is significantly reduced. It can effectively solve a series of problems existing in traditional phosphorus-based flame retardants, so it has great application prospects.

[0005] Chinese Patent CN110591106A obtained a phosphorus-silicon synergistic flame retardant with a hyperbranched structure by reacting alkoxysilane, trialkyl phosphate, and diol in a certain molar ratio. This flame retardant has the characteristics of low viscosity and many terminal active functional groups, and can be evenly dispersed in the material matrix. The flame retardant elements such as phosphorus and silicon contained in it can produce a synergistic effect, making it have good flame retardant effects in both the condensed phase and the gas phase, and has broad application prospects in the flame retardancy of coatings, textiles, furniture, buildings, and thermosetting and thermoplastic resins. However, due to the introduction of phosphate structures and C-O-C bonds into the phosphorus-silicon synergistic flame retardant, the ceramization effect and temperature resistance of the flame retardant itself are weakened, resulting in a low char residue rate of the flame retardant and the inability to effectively form a dense carbon layer in the polymer. Therefore, the improvement of the flame retardant, smoke suppression, and ablation resistance properties of polymer materials is relatively limited.

[0006] Chinese Patent CN112625244A prepared a series of phosphorus-silicon synergistic flame retardants with hyperbranched structures by co-condensing diols and trisiloxanes. Among them, the hyperbranched phosphorus-nitrogen-containing organosilicon flame retardant integrates acid source, carbon source, and gas source at the molecular level, with higher flame retardant efficiency. When applied to transparent flame retardant coatings, especially waterborne transparent flame retardant coatings, it can effectively improve the flame retardant performance of plastics. However, the Si-O-C bond formed by the condensation of carbon hydroxyl and silane oxy groups is a reversible bond and will hydrolyze and depolymerize back into small molecule diols and small molecule silane coupling agents in a humid environment. Therefore, the hyperbranched phosphorus-silicon synergistic flame retardant prepared by this method has poor storage stability. Although it has a certain flame retardant effect, it cannot effectively solve the defects of traditional phosphorus-based flame retardants, such as high migration rate, easy water solubility, and poor high-temperature stability.

[0007] Chinese Patent CN118459767A prepares a silane coupling agent containing phosphorus elements by reacting a traditional phosphorus-based flame retardant with a silane coupling agent, and then reacts with an aminopropyl silane coupling agent under alkaline conditions to obtain a reactive silicon-phosphorus-nitrogen synergistic high-efficiency flame retardant powder. Adding it as a flame retardant filler to polyurea materials has high reactive activity, can effectively improve the flame retardancy of polyurea materials, and has excellent thermal stability. However, as a solid flame retardant, the reactive silicon-phosphorus-nitrogen synergistic high-efficiency flame retardant is difficult to use in transparent polymer material systems. At the same time, the presence of amino groups makes it weakly basic, and its long-term presence in some polymer materials may accelerate material aging, resulting in a decrease in the mechanical properties of the materials, thus limiting its application scope.

[0008] In summary, at the present stage, the research on silicon-phosphorus synergistic flame retardants is difficult to combine the characteristics of high fluidity, low viscosity, high thermal stability, and ablation resistance. The low-viscosity liquid silicon-phosphorus synergistic flame retardant obtained by introducing phosphate esters into the silicon oxygenane molecular structure can improve the problems of easy water solubility, high migration rate, and poor compatibility of phosphorus-based flame retardants, but the improvement of the thermal stability and ablation resistance of materials is limited. The silicon-phosphorus synergistic flame retardant obtained by connecting the flame retardant to the surface of the silicon oxygenane molecular structure has excellent thermal stability and flame retardant effect, but it presents a solid powder state, losing the fluidity and compatibility of the phosphorus-based flame retardant itself, restricting its scope of application. Therefore, the development of a new type of silicon-phosphorus synergistic flame retardant with high fluidity, high compatibility, ablation resistance, and excellent thermal stability will be an important step in the development of the silicon-phosphorus synergistic flame retardant system. Summary of the Invention

[0009] Object of the Invention: In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a low-viscosity expandable flame retardant phosphorus hybrid hyperbranched organosilicon polymer, and another object of the present invention is to provide a preparation method of a low-viscosity expandable flame retardant phosphorus hybrid hyperbranched organosilicon polymer.

[0010] Technical Solution: A low-viscosity expandable flame retardant phosphorus hybrid hyperbranched organosilicon polymer according to the present invention is formed by the controlled hydrolysis and condensation of a phosphorus-modified silane monomer and a silane monomer under acidic conditions to form a hyperbranched organosilicon polymer with a highly branched and non-fully regular three-dimensional network structure; the hyperbranched organosilicon polymer has a Si-O-Si main chain structure and is rich in phosphorus on the side chains.

[0011] A preparation method of a low-viscosity expandable flame retardant phosphorus hybrid hyperbranched organosilicon polymer according to the present invention includes the following steps:

[0012] Step 1, mix an alkaline catalyst, a phosphorus source, a silane coupling agent containing a glycidyl ether group with a solvent, react at 30 - 150 °C, and purify to obtain a phosphorus-modified silane monomer; the ring-opening reaction of the epoxy group caused by the attack of the hydroxyl group on the glycidyl ether in an alkaline environment;

[0013] Step 2: Mix an acidic catalyst, water, a solvent, a silane monomer, and a phosphorus-modified silane monomer, react at 60-100 °C, and purify to obtain a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer. Step 2 is a controlled hydrolysis and self-condensation reaction of the silane monomer in an acidic environment.

[0014] Further, in Step 1, the basic catalyst is any one of triethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundec-7-ene, 4-dimethylaminopyridine, diethylenetriamine, and triethylamine.

[0015] Further, in Step 1, the phosphorus source is pentaerythritol phosphate, and the silane coupling agent containing a glycidyl ether group is one or more of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. The main function of the phosphorus source is to provide the phosphorus element and the hydroxyl functional group required for the ring-opening reaction of the epoxy group.

[0016] Further, in Step 1, the molar ratio of the phosphorus source, the silane coupling agent containing a glycidyl ether group, and the solvent is 1:1:1-3, and the addition amount of the basic catalyst is 0.1-1 wt% of the total mass of the phosphorus source, the silane coupling agent containing a glycidyl ether group, and the solvent.

[0017] Further, in Step 1, the molecular structural formula of the phosphorus-modified silane monomer is:

[0018]

[0019] Among them, R1 is at least one of methyl and ethyl.

[0020] Further, in Step 2, the molecular structural formula of the silane monomer is:

[0021]

[0022] Among them, R1 is at least one of methyl or ethyl, and R2 is one or more of anilinomethyl, aminopropyl, mercaptopropyl, acryloxypropyl, methyl, phenyl, vinyl, glycidyl ether propyl, and chloromethyl.

[0023] Further, in Step 2, the molar ratio of the phosphorus-modified silane monomer to the silane monomer is 0.01-0.99:0.99-0.01, and the molar ratio of the silane monomer to water is 1:0.5-2.

[0024] Further, in Step 2, the acidic catalyst is one or more of formic acid, hydrochloric acid, acetic acid, sulfuric acid, nitric acid, and phosphoric acid.

[0025] Further, the solvent is one or more of ethanol, methanol, toluene, xylene, dichloromethane, tetrahydrofuran, ethyl acetate, methyl acetate, acetone, dioxane, and carbon tetrachloride.

[0026] Further, the synthesis reaction formula is:

[0027]

[0028] Among them, R is at least one of aniline methyl, amino, mercapto, acryloyloxy, vinyl, glycidyl ether group, methyl, phenyl, and chloromethyl.

[0029] Preparation principle: Through molecular design, phosphorus elements are embedded in the hyperbranched organosilicon skeleton in the form of covalent bonds to construct a phosphorus-silicon synergistic flame retardant system. Under alkaline conditions, pentaerythritol phosphate reacts with a silane coupling agent containing a glycidyl ether group to generate a phosphorus-modified intermediate, and then through controlled hydrolysis in an acidic environment, it undergoes a condensation reaction with a multi-functional silane coupling agent to form a polymer material with a three-dimensional highly branched structure. The prepared phosphorus hybrid hyperbranched organosilicon polymer combines the advantages of the hyperbranched organosilicon polymer, such as strong structural designability, rich terminal active functional groups, low viscosity, high fluidity, high temperature resistance, and high char residue rate, with the high-efficiency flame retardant characteristics brought by the condensed-phase and gas-phase dual flame retardant mechanisms of phosphorus-based flame retardants.

[0030] Beneficial effects: Compared with the prior art, the present invention has the following significant characteristics:

[0031] 1. It is expected to provide an innovative solution that is efficient, environmentally friendly, and multi-functional for high-end flame retardant materials in fields such as new energy batteries and aerospace;

[0032] 2. Excellent flame retardant performance. The synergistic effect of silicon and phosphorus enables the material to exhibit excellent flame retardant effects from two routes. In the gas phase, the presence of phosphorus elements can effectively quench free radicals and block the chain reaction of combustion. At the same time, silicon particles can effectively adsorb harmful gases and reduce the harm of toxic gases generated by combustion. In the condensed phase, the highly branched structure of the hyperbranched organosilicon polymer can form a stable and dense carbonized layer during combustion, preventing the release of combustible gases and the entry of combustion-supporting components, further enhancing the flame retardant effect, so that the introduction of the new phosphorus hybrid hyperbranched organosilicon polymer into polymer materials can achieve a higher flame retardant grade and lower smoke generation under the premise of a lower addition amount;

[0033] 3. Stronger stability: The existence of the hyperbranched structure and the introduction of Si-O bonds enhance the structural stability and hydrophobicity of the material, making it difficult to decompose at high temperatures and dissolve in water, thus maintaining performance stability for a longer time. As a result, the phosphorus hybrid hyperbranched organosilicon polymer exhibits more excellent thermal stability, water resistance, and anti-aging properties under harsh environments such as high temperature and high humidity, and can maintain a longer effective period under extreme conditions.

[0034] 4. Higher green environmental protection: The phosphorus element is fixed in the organosilicon structure, avoiding environmental pollution during the decomposition of traditional flame retardants. The high stability of the material also reduces resource consumption, making the phosphorus hybrid hyperbranched organosilicon polymer not easy to migrate and escape from the polymer during actual application, reducing environmental pollution and avoiding the problem of traditional phosphorus-based flame retardants possibly releasing harmful substances.

[0035] 5. Excellent compatibility and mechanical properties: Thanks to the uniform particle size distribution at the nanoscale and the rich active functional groups at the ends of the hyperbranched organosilicon polymer, it can be uniformly dispersed in traditional polymer materials and combined through chemical bonds or physical interactions, thus showing excellent compatibility. At the same time, the three-dimensional highly branched structure of the hyperbranched polymer forms physical entanglement or chemical cross-linking with the polymer matrix, which can further increase the cross-linking density of the polymer material and maintain the excellent mechanical properties of the polymer material, making the phosphorus hybrid hyperbranched organosilicon polymer not cause a decrease in the mechanical properties of traditional polymer materials during actual application and showing higher reliability.

[0036] 6. Efficient and environmentally friendly preparation process: Phosphorus elements are directly introduced into the organosilicon structure through ring-opening reaction of epoxy and controlled hydrolysis and condensation, simplifying the preparation process and reducing the dependence on harmful chemical reagents, making the phosphorus hybrid hyperbranched organosilicon polymer more environmentally friendly in actual production and reducing environmental pollution.

[0037] 7. Broad application prospects: In the fields of electrical equipment, building materials, aerospace, etc., the excellent flame retardant performance, thermal stability, and environmental protection of the new phosphorus hybrid hyperbranched organosilicon polymer make it an ideal choice for high-temperature and high-safety scenarios. With the improvement of environmental protection requirements, the environmental protection and high-performance characteristics of this material will further promote its application in more fields and contribute to the sustainable development needs. Brief Description of the Drawings

[0038] Figure 1 is a physical picture of the phosphorus hybrid hyperbranched organosilicon polymer;

[0039] Figure 2 is the infrared and nuclear magnetic spectra of the phosphorus hybrid hyperbranched organosilicon polymer obtained in Example 1, where a is the infrared spectrum and b is the nuclear magnetic resonance silicon spectrum;

[0040] Figure 3 It is the thermal stability test diagram of the phosphorus hybrid hyperbranched organosilicon polymer obtained in Example 2;

[0041] Figure 4 It is the high-temperature flame ablation diagram of the phosphorus hybrid hyperbranched organosilicon polymer obtained in Example 2 at different times. Among them, a is 0s, b is 6s, c is 12s, d is 18s, e is 24s, and f is 30s;

[0042] Figure 5 It is the physical diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane obtained in Example 3;

[0043] Figure 6 It is the physical diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane with different addition amounts in Example 3. Among them, (a) is the addition amount of 10% in the polyurethane material, (b) is the addition amount of 20% in the polyurethane material, and (c) is the addition amount of 30% in the polyurethane material;

[0044] Figure 7 It is the mechanical property test diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane in Example 4;

[0045] Figure 8 It is the adhesion property test diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane in Example 5;

[0046] Figure 9 It is the adhesion property test diagram of the modified polyurethane material under high-temperature aging in Example 5;

[0047] Figure 10 It is the adhesion property test diagram of the modified polyurethane material under high-humidity environment aging in Example 5;

[0048] Figure 11 It is the contact angle test diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane in Example 6 for different reagents. Among them, a is diiodomethane and b is water;

[0049] Figure 12 It is the water absorption rate and oil absorption rate test diagram of the modified polyurethane material in Example 6. Among them, a is the water absorption rate diagram and b is the oil absorption rate diagram;

[0050] Figure 13 It is the thermal stability test diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane in Example 7;

[0051] Figure 14 It is the oxygen index test diagram of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane in Example 7;

[0052] Figure 15It is the cone calorimeter test chart of the phosphorus-hybridized hyperbranched organosilicon polymer modified polyurethane in Example 7. Among them, a is the smoke density data of the material when the addition amount is 40 wt%, b is the smoke density data of the material when the addition amount is 0 wt%, c is the heat release data of the material when the addition amount is 40 wt%, and d is the heat release data of the material when the addition amount is 0 wt%.

[0053] Figure 16 It is the vertical burning test chart of the phosphorus-hybridized hyperbranched organosilicon polymer modified polyurethane with different addition amounts of hyperbranched organosilicon in Example 8. Among them, a is the addition amount of 0 wt%, b is the addition amount of 20 wt%, and c is 40 wt%.

[0054] Figure 17 It is the physical diagram of the combustion residue of the phosphorus-hybridized hyperbranched organosilicon polymer modified polyurethane in Example 8. Among them, a is the physical diagram of the combustion residue when the addition amount is 0 wt%, b is the physical diagram of the combustion residue when the addition amount is 2 wt%, and c is the physical diagram of the combustion residue when the addition amount is 40 wt%.

[0055] Figure 18 It is the physical diagram of the silicone-based flame retardant SFR-100 modified polyurethane material in Comparative Example 1. Among them, a is the physical diagram after mixing polyurethane with the silicone-based flame retardant SFR-100, and b is the physical diagram after curing the mixture of polyurethane and the silicone-based flame retardant SFR-100.

[0056] Figure 19 It is the physical diagram of the phosphorus-based flame retardant DMMP modified polyurethane material with different ratios in Comparative Example 2. Among them, (a) is the addition amount of 10% in the material, (b) is the addition amount of 20% in the material, and (c) is the addition amount of 30% in the material.

[0057] Figure 20 It is the contact angle test chart of the phosphorus-based flame retardant TEP modified polyurethane material in Comparative Example 3 with different reagents. Among them, a is diiodomethane and b is water.

[0058] Figure 21 It is the water absorption and oil absorption test chart of the phosphorus-based flame retardant TEP modified polyurethane material in Comparative Example 3. Among them, a is the water absorption chart and b is the oil absorption chart.

[0059] Figure 22 It is the vertical burning test chart of the phosphorus-based flame retardant DOPO modified polyurethane material with different flame retardant addition ratios in Comparative Example 4. Among them, a is the physical diagram of the combustion residue when the addition amount is 0 wt%, b is the physical diagram of the combustion residue when the addition amount is 20 wt%, and c is the physical diagram of the combustion residue when the addition amount is 40 wt%.

[0060] Figure 23It is a physical diagram of the combustion residues of DOPO-modified polyurethane materials with different addition amounts of phosphorus-based flame retardants in Comparative Example 4. Among them, a is the DOPO addition amount of 0 wt%, b is the DOPO addition amount of 20 wt%, and c is the DOPO addition amount of 40 wt%. Detailed implementation manners

[0061] The materials, reagents, instruments, etc. used in the following examples can be obtained from commercial channels without special instructions. The experimental methods without specific conditions in the examples usually follow conventional conditions or the conditions recommended by the manufacturer.

[0062] The structural formula of pentaerythritol phosphate is:

[0063]

[0064] The structure of γ-glycidyletheroxypropyltrimethoxysilane is:

[0065]

[0066] The structure of γ-glycidyletheroxypropyltriethoxysilane is:

[0067]

[0068] Example 1

[0069] A preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer, comprising the following steps:

[0070] (1) The preparation step of the phosphorus-modified silane monomer is as follows: Under the protection of an inert gas, 1 mol of pentaerythritol phosphate, 1 mol of tetrahydrofuran solvent, 1 mol of glycidyletherpropyltrimethoxysilane, and 2 wt% of triethylamine catalyst are added to a three-necked flask equipped with a condenser and a mechanical stirrer. After stirring evenly at room temperature, it is slowly heated to 100 °C and reacted for 1 h.

[0071] (2) The purification step of the phosphorus-modified silane monomer is as follows: After turning off the heating and naturally cooling to 50 °C, the residual tetrahydrofuran and triethylamine in the reaction system are removed by a thin-film evaporator to obtain a light yellow transparent liquid with low viscosity, which is the phosphorus-modified silane monomer.

[0072] (3) The preparation step of the phosphorus hybrid hyperbranched organosilicon polymer: Under the protection of an inert gas, 0.99 mol of the phosphorus-modified silane monomer, 0.01 mol of methyltrimethoxysilane, 1.3 mol of deionized water, and 3 mol of ethanol solvent are added to a three-necked flask equipped with a condenser and a mechanical stirrer. After hydrolysis reaction at room temperature for 1 h, 0.5 wt% of hydrochloric acid catalyst is added and stirred evenly, and then slowly heated to 70 °C and reacted for 4 h.

[0073] (4) The purification step of the phosphorus-hybridized hyperbranched organosilicon polymer is as follows: Turn off the heating and let it cool naturally to 50 °C. Use a rotary evaporator to remove the residual ethanol, methanol, water, and hydrochloric acid in the reaction system to obtain a low-viscosity light yellow transparent liquid. As Figure 1 shown, it is the low-viscosity intumescent flame-retardant phosphorus-hybridized hyperbranched organosilicon polymer.

[0074] The phosphorus-hybridized hyperbranched organosilicon polymer prepared in this example was tested for room temperature viscosity. Using a rotary viscometer, it was tested according to the viscosity measurement method of GB-T 10247-2008, and the shear viscosity was 319 mPa·s.

[0075] Figure 2 are the infrared spectrum before and after the synthesis of the phosphorus-hybridized hyperbranched organosilicon polymer and the nuclear magnetic resonance silicon spectrum of the phosphorus-hybridized hyperbranched organosilicon polymer, which prove that the prepared phosphorus-hybridized hyperbranched organosilicon polymer exhibits a high degree of branching.

[0076] Example 2

[0077] A preparation method of a phosphorus-hybridized hyperbranched organosilicon polymer with ablation resistance and high char yield includes the following steps:

[0078] (1) The preparation step of the phosphorus-modified silane monomer is as follows: Under the protection of an inert gas, add 1 mol of pentaerythritol phosphate, 2 mol of ethyl acetate solvent, 1 mol of glycidyl ether propyltrimethoxysilane, and 1 wt% of 2,4,6-tris(dimethylaminomethyl)phenol catalyst into a three-necked flask equipped with a condenser and a mechanical stirrer. After stirring evenly at room temperature, slowly heat to 80 °C and react for 20 min.

[0079] (2) The purification step of the phosphorus-modified silane monomer is as follows: After turning off the heating and letting it cool naturally to 80 °C, use a vacuum distillation device to remove the residual ethyl acetate and 2,4,6-tris(dimethylaminomethyl)phenol in the reaction system to obtain a high-viscosity yellow transparent liquid, which is the phosphorus-modified silane monomer.

[0080] (3) The preparation step of the phosphorus-hybridized hyperbranched organosilicon polymer: Under the protection of an inert gas, add 0.3 mol of phosphorus-modified silane monomer, 0.7 mol of methyltrimethoxysilane, 1.5 mol of deionized water, and 2 mol of methanol solvent into a three-necked flask equipped with a condenser and a mechanical stirrer. After hydrolysis reaction at room temperature for 2 h, add 1 wt% acetic acid catalyst and stir evenly, then slowly heat to 100 °C and react for 6 h.

[0081] (4) The purification step of the phosphorus-hybridized hyperbranched organosilicon polymer is as follows: Turn off the heating and let it cool naturally to 60 °C. Use a rotary evaporator to remove the residual methanol, water, and acetic acid in the reaction system to obtain a medium-viscosity light yellow transparent liquid, which is the phosphorus-hybridized hyperbranched organosilicon polymer.

[0082] The room-temperature viscosity of the phosphorus-hybridized hyperbranched organosilicon polymer prepared in this example was tested. Using a rotational viscometer, the shear viscosity was measured according to the viscosity measurement method of GB-T 10247-2008, and the shear viscosity was 5500 mPa·s.

[0083] Figure 3 This is the thermal stability test diagram of the phosphorus-hybridized hyperbranched organosilicon polymer. It can be seen from the figure that the initial thermal decomposition temperature of the prepared product exceeds 200 °C, and at the same time, its char residue rate at 1000 °C exceeds 55%, showing the characteristics of high temperature resistance and high char residue.

[0084] Figure 4 This is the high-temperature ablation diagram of the phosphorus-hybridized hyperbranched organosilicon polymer. It can be seen that the prepared product rapidly expands to form a dense carbon layer under the ablation of a 1000 °C high-temperature spray gun, thus showing an efficient flame retardant effect.

[0085] Example 3

[0086] A preparation method of a highly compatible phosphorus-hybridized hyperbranched organosilicon polymer includes the following steps:

[0087] (1) The preparation step of the phosphorus-modified silane monomer is as follows: Under the protection of an inert gas, add 1 mol of pentaerythritol phosphate, 1 mol of dioxane solvent, 1 mol of glycidyl ether propyltriethoxysilane, and 0.5 wt% of 1,8-diazabicycloundec-7-ene catalyst into a three-necked flask equipped with a condenser and a mechanical stirrer. After stirring evenly at room temperature, slowly heat to 50 °C and react for 6 h.

[0088] (2) The purification step of the phosphorus-modified silane monomer is as follows: After turning off the heating and naturally cooling to 30 °C, use a vacuum distillation device to remove the residual dioxane and 1,8-diazabicycloundec-7-ene in the reaction system to obtain a low-viscosity yellow transparent liquid, which is the phosphorus-modified silane monomer.

[0089] (3) The preparation step of the phosphorus-hybridized hyperbranched organosilicon polymer: Under the protection of an inert gas, add 0.4 mol of phosphorus-modified silane monomer, 0.6 mol of phenyltrimethoxysilane, 1.4 mol of deionized water, and 3 mol of methyl acetate solvent into a three-necked flask equipped with a condenser and a mechanical stirrer. After hydrolysis reaction at room temperature for 30 min, add 0.3 wt% dilute sulfuric acid catalyst, stir evenly, and slowly heat to 60 °C and react for 3 h.

[0090] (4) The purification step of the phosphorus-hybridized hyperbranched organosilicon polymer is as follows: After turning off the heating and naturally cooling to 40 °C, use a rotary evaporator to remove the residual methyl acetate, ethanol, water, and sulfuric acid in the reaction system to obtain a low-viscosity light yellow transparent liquid, which is the phosphorus-hybridized hyperbranched organosilicon polymer.

[0091] The room-temperature viscosity of the phosphorus-hybridized hyperbranched organosilicon polymer prepared in this example was measured using a rotational viscometer according to the viscosity measurement method of GB-T 10247-2008, and the shear viscosity was 1034 mPa·s.

[0092] The implementation method of the phosphorus-hybridized hyperbranched organosilicon polymer modified polyurethane elastomer material is as follows:

[0093] Mix the phosphorus-hybridized hyperbranched organosilicon polymer, polyurethane prepolymer, and MOCA curing agent in a ratio of 0, 10, 20, 30, 40:80:20, mechanically stir at 3000 rpm for 5 minutes under vacuum conditions to ensure uniform dispersion, and then perform degassing treatment; subsequently, introduce the mixture into the mold through casting, spraying, or injection molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the phosphorus-hybridized hyperbranched organosilicon polymer modified polyurethane elastomer material.

[0094] From Figure 5 、 Figure 6 it can be seen that when the addition amount (mass percentage) of the prepared phosphorus-hybridized hyperbranched organosilicon polymer in the polyurethane material is less than 10 wt%, it still shows high transparency after curing, and even when the addition amount reaches 30 wt%, it still does not affect the normal molding and curing of the material, and shows excellent compatibility with polyurethane.

[0095] Example 4

[0096] A preparation method of a flame-retardant and high-strength phosphorus-hybridized hyperbranched organosilicon polymer, comprising the following steps:

[0097] (1) The preparation step of the phosphorus-modified silane monomer is as follows: Under the protection of an inert gas, add 1 mol of pentaerythritol phosphate, 1 mol of toluene solvent, 1 mol of glycidyl ether propyltrimethoxysilane, and 0.3 wt% of 4-dimethylaminopyridine catalyst into a three-necked flask equipped with a condenser and mechanical stirrer. After stirring evenly at room temperature, slowly heat to 90 °C and react for 1 h.

[0098] (2) The purification step of the phosphorus-modified silane monomer is as follows: After turning off the heating and naturally cooling to 60 °C, use a thin-film evaporator to remove the residual toluene and 4-dimethylaminopyridine in the reaction system to obtain a highly viscous yellow transparent liquid, which is the phosphorus-modified silane monomer.

[0099] (3) The preparation step of the phosphorus-hybridized hyperbranched organosilicon polymer: Under the protection of an inert gas, add 0.2 mol of phosphorus-modified silane monomer, 0.8 mol of aniline methyltriethoxysilane, 1.2 mol of deionized water, and 3 mol of xylene solvent into a three-necked flask equipped with a condenser and mechanical stirrer. After hydrolysis reaction at room temperature for 1 h, add 0.1 wt% dilute nitric acid catalyst and stir evenly, then slowly heat up to 80 °C and react for 4 h.

[0100] (4) The purification step of the phosphorus - hybridized hyperbranched organosilicon polymer is as follows: Turn off the heating and let it cool naturally to 50 °C. Use a rotary evaporator to remove the remaining xylene, ethanol, water, and nitric acid in the reaction system, and obtain a medium - viscosity light - yellow transparent liquid, which is the phosphorus - hybridized hyperbranched organosilicon polymer.

[0101] The phosphorus - hybridized hyperbranched organosilicon polymer prepared in this example was tested for room - temperature viscosity. Using a rotary viscometer, according to the viscosity measurement method of GB - T 10247 - 2008, the shear viscosity was 6542 mPa·s.

[0102] The implementation method of the phosphorus - hybridized hyperbranched organosilicon polymer - modified polyurethane elastomer material is as follows:

[0103] Mix the phosphorus - hybridized hyperbranched organosilicon polymer, polyurethane prepolymer, and curing agent in a ratio of 0, 10, 20, 30, 40:80:20. Stir mechanically at 3000 rpm for 5 minutes under vacuum conditions to ensure uniform dispersion, and then perform degassing treatment; Subsequently, introduce the mixture into a mold through casting, spraying, or injection - molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the phosphorus - hybridized hyperbranched organosilicon polymer - modified polyurethane elastomer material.

[0104] Figure 7 It can be seen that when the addition amount of the phosphorus - hybridized hyperbranched organosilicon polymer in the polyurethane elastomer is below 20%, the high mechanical properties of the polyurethane elastomer material are maintained, which is significantly improved compared with traditional phosphorus - based flame retardants.

[0105] Example 5

[0106] A preparation method of an adhesion - enhanced, flame - retardant phosphorus - hybridized hyperbranched organosilicon polymer, comprising the following steps:

[0107] (1) The preparation step of the phosphorus - modified silane monomer is as follows: Under the protection of an inert gas, add 1 mol of pentaerythritol phosphate, 3 mol of carbon tetrachloride solvent, 1 mol of glycidyl ether propyltrimethoxysilane, and 1 wt% of diethylenetriamine catalyst into a three - necked flask equipped with a condenser and a mechanical stirrer. Stir evenly at room temperature and then slowly heat to 150 °C and react for 10 min.

[0108] (2) The purification step of the phosphorus - modified silane monomer is as follows: After turning off the heating and letting it cool naturally to 60 °C, use the vacuum distillation method to remove the remaining carbon tetrachloride and diethylenetriamine in the reaction system, and obtain a low - viscosity light - yellow transparent liquid, which is the phosphorus - modified silane monomer.

[0109] (3) Preparation steps of phosphorus - hybrid hyperbranched organosilicon polymer: Under the protection of inert gas, add 0.4 mol of phosphorus - modified silane monomer, 0.3 mol of glycidyl ether propyltrimethoxysilane, 0.3 mol of acryloxypropyltrimethoxysilane, 1.3 mol of deionized water, and 2 mol of dichloromethane solvent into a three - necked flask equipped with a condenser and a mechanical stirrer. After hydrolysis reaction at room temperature for 1 h, add 1 wt% formic acid catalyst and stir evenly. Then slowly heat up to 70 °C and react for 4 h.

[0110] (4) Purification steps of phosphorus - hybrid hyperbranched organosilicon polymer: Turn off the heating and let it cool naturally to 50 °C. Use a rotary evaporator to remove the remaining dichloromethane, methanol, water, and formic acid in the reaction system to obtain a low - viscosity light - yellow transparent liquid, which is the phosphorus - hybrid hyperbranched organosilicon polymer.

[0111] The phosphorus - hybrid hyperbranched organosilicon polymer prepared in this example was tested for room - temperature viscosity. Using a rotary viscometer and according to the viscosity measurement method of GB - T 10247 - 2008, the shear viscosity was 379 mPa·s.

[0112] The implementation method of the phosphorus - hybrid hyperbranched organosilicon polymer - modified polyurethane adhesive is as follows:

[0113] Mix the phosphorus - hybrid hyperbranched organosilicon polymer, polyurethane prepolymer, and curing agent in a ratio of 0, 10, 20, 30, 40:80:20. Stir mechanically at 3000 rpm for 5 minutes under vacuum conditions to ensure uniform dispersion, and then perform degassing treatment; Subsequently, apply the adhesive to the surface of the adherend by spraying or scraping, and cure at room temperature to 100 °C for 48 hours.

[0114] Figure 8 It can be seen that the prepared phosphorus - hybrid hyperbranched organosilicon polymer shows a relatively high bonding strength after copolymerization with the polyurethane material, and the bonding strength to different substrates exceeds 15 MPa.

[0115] Figure 9 、 Figure 10 It can be seen that the introduction of the phosphorus - hybrid hyperbranched organosilicon polymer improves the aging resistance of the polyurethane adhesive, and the bonding strength shows no obvious decrease after aging in water and at high temperature.

[0116] Example 6

[0117] A preparation method of a chemical - resistant phosphorus - hybrid hyperbranched organosilicon polymer, comprising the following steps:

[0118] (1) The preparation steps of the phosphorus-modified silane monomer are as follows: Under the protection of an inert gas, add 1 mol of pentaerythritol phosphate, 2 mol of acetone solvent, 1 mol of glycidyl ether propyltriethoxysilane, and 1 wt% of triethylamine catalyst into a three-necked flask equipped with a condenser and a mechanical stirrer. After stirring evenly at room temperature, slowly heat to 30 °C and react for 24 h.

[0119] (2) The purification steps of the phosphorus-modified silane monomer are as follows: At 30 °C, use the vacuum distillation method to remove the residual acetone and triethylamine in the reaction system to obtain a highly viscous yellow transparent liquid, which is the phosphorus-modified silane monomer.

[0120] (3) The preparation steps of the phosphorus-hybrid hyperbranched organosilicon polymer: Under the protection of an inert gas, add 0.5 mol of phosphorus-modified silane monomer, 0.5 mol of vinyltrimethoxysilane, 1.5 mol of deionized water, and 3 mol of acetone solvent into a three-necked flask equipped with a condenser and a mechanical stirrer. After hydrolyzing at room temperature for 1 h, add 0.4 wt% of phosphoric acid catalyst and stir evenly, then slowly heat up to 70 °C and react for 4 h.

[0121] (4) The purification steps of the phosphorus-hybrid hyperbranched organosilicon polymer are as follows: Turn off the heating and let it cool naturally to 50 °C, use a rotary evaporator to remove the residual acetone, methanol, water, and phosphoric acid in the reaction system to obtain a medium-high viscosity yellow transparent liquid, which is the phosphorus-hybrid hyperbranched organosilicon polymer.

[0122] The phosphorus-hybrid hyperbranched organosilicon polymer prepared in this example was tested for room temperature viscosity. Using a rotational viscometer, according to the viscosity measurement method of GB-T 10247-2008, the shear viscosity was 8547 mPa·s.

[0123] The implementation method of the phosphorus-hybrid hyperbranched organosilicon polymer modified polyurethane elastomer material is as follows:

[0124] Mix the phosphorus-hybrid hyperbranched organosilicon polymer, polyurethane prepolymer, and curing agent in a ratio of 0, 10, 20, 30, 40:80:20. Under vacuum conditions, mechanically stir at 3000 rpm for 5 minutes. After ensuring uniform dispersion, perform degassing treatment; then introduce the mixture into the mold through casting, spraying, or injection molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the phosphorus-hybrid hyperbranched organosilicon polymer modified polyurethane elastomer material.

[0125] Figure 11 It can be seen that the modified polyurethane elastomer shows a relatively high contact angle for both oily reagents and aqueous reagents.

[0126] Figure 12 It can be seen that the modified polyurethane elastomer shows a relatively low water absorption and oil absorption rate after being soaked in kerosene and water, and has excellent chemical resistance.

[0127] Example 7

[0128] A preparation method of an efficient flame-retardant phosphorus hybrid hyperbranched organosilicon polymer, comprising the following steps:

[0129] (1) The preparation step of the phosphorus-modified silane monomer is as follows: Under the protection of inert gas, add 1 mol of pentaerythritol phosphate, 3 mol of dioxane solvent, 1 mol of glycidyl ether propyltrimethoxysilane and 3 wt% of triethylamine catalyst into a three-necked flask equipped with a condenser and mechanical stirring. After stirring evenly at room temperature, slowly heat to 50 °C and react for 12 h.

[0130] (2) The purification step of the phosphorus-modified silane monomer is as follows: At 50 °C, use vacuum distillation to remove the residual dioxane and triethylamine in the reaction system, and the high-viscosity yellow transparent liquid obtained is the phosphorus-modified silane monomer.

[0131] (3) The preparation step of the phosphorus hybrid hyperbranched organosilicon polymer: Under the protection of inert gas, add 0.5 mol of phosphorus-modified silane monomer, 0.5 mol of chloromethyltrimethoxysilane, 1.3 mol of deionized water, and 2 mol of ethanol solvent into a three-necked flask equipped with a condenser and mechanical stirring. After hydrolysis reaction at room temperature for 1 h, add 1 wt% hydrochloric acid catalyst and stir evenly, then slowly heat up to 70 °C and react for 6 h.

[0132] (4) The purification step of the phosphorus hybrid hyperbranched organosilicon polymer is as follows: Turn off the heating and let it cool naturally to 50 °C. Use a rotary evaporator to remove the residual ethanol, methanol, water and hydrochloric acid in the reaction system, and the medium-high viscosity yellow transparent liquid obtained is the phosphorus hybrid hyperbranched organosilicon polymer.

[0133] The phosphorus hybrid hyperbranched organosilicon polymer prepared in this example was subjected to a room temperature viscosity test. Using a rotational viscometer, according to the viscosity measurement method of GB-T 10247-2008, the shear viscosity was 5987 mPa·s.

[0134] The implementation method of the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane elastomer material is as follows:

[0135] Mix the phosphorus hybrid hyperbranched organosilicon polymer, polyurethane prepolymer and curing agent in a ratio of 0, 10, 20, 30, 40:80:20, stir mechanically at 3000 rpm for 5 minutes under vacuum conditions to ensure uniform dispersion and then perform defoaming treatment; Subsequently, introduce the mixture into the mold through casting, spraying or injection molding process, and cure at room temperature to 100 °C for 48 hours to obtain the phosphorus hybrid hyperbranched organosilicon polymer modified polyurethane elastomer material.

[0136] Figure 13It can be seen that adding 10% of the phosphorus hybridized hyperbranched organosilicon polymer can effectively improve the temperature resistance and ablation resistance of the polyurethane elastomer, and the char residue rate is significantly increased.

[0137] Figure 14 、 Figure 15 It can be seen that the oxygen index of the modified polyurethane elastomer material is significantly increased, and the heat release and smoke density during combustion are effectively inhibited, showing excellent flame retardant properties.

[0138] Example 8

[0139] A preparation method of a reactive and highly flame retardant phosphorus hybridized hyperbranched organosilicon polymer, comprising the following steps:

[0140] (1) The preparation step of the phosphorus modified silane monomer is as follows: Under the protection of inert gas, add 1 mol of pentaerythritol phosphate, 3 mol of tetrahydrofuran solvent, 1 mol of glycidyl ether propyltrimethoxysilane and 1 wt% of triethylamine catalyst into a three-necked flask equipped with a condenser and a mechanical stirrer. After stirring evenly at room temperature, slowly heat to 120 °C and react for 1 h.

[0141] (2) The purification step of the phosphorus modified silane monomer is as follows: Remove the heating device, naturally cool to 60 °C, and use a thin film evaporator to remove the residual tetrahydrofuran and triethylamine in the reaction system to obtain a highly viscous yellow transparent liquid, which is the phosphorus modified silane monomer.

[0142] (3) The preparation step of the phosphorus hybridized hyperbranched organosilicon polymer: Under the protection of inert gas, add 0.7 mol of phosphorus modified silane monomer, 0.3 mol of mercaptopropyltrimethoxysilane, 1.3 mol of deionized water, and 3 mol of methyl acetate solvent into a three-necked flask equipped with a condenser and a mechanical stirrer. After hydrolyzing at room temperature for 1 h, add 1 wt% hydrochloric acid catalyst and stir evenly, then slowly heat up to 70 °C and react for 3 h.

[0143] (4) The purification step of the phosphorus hybridized hyperbranched organosilicon polymer is as follows: Turn off the heating and naturally cool to 60 °C, and use a rotary evaporator to remove the residual methyl acetate, methanol, water and hydrochloric acid in the reaction system to obtain a medium-high viscosity yellow transparent liquid, which is the phosphorus hybridized hyperbranched organosilicon polymer.

[0144] The phosphorus hybridized hyperbranched organosilicon polymer prepared in this example was tested for room temperature viscosity, and the shear viscosity was 4572 mPa·s by using a rotational viscometer according to the viscosity measurement method of GB-T 10247-2008.

[0145] The implementation method of the phosphorus hybridized hyperbranched organosilicon polymer modified polyurethane elastomer material is as follows:

[0146] The phosphorous hybrid hyperbranched organosilicon polymer, polyurethane prepolymer, and curing agent are mixed in a ratio of 0, 10, 20, 30, 40:80:20, mechanically stirred at 3000 rpm for 5 minutes under vacuum conditions to ensure uniform dispersion, and then degassed; subsequently, the mixture is introduced into a mold through casting, spraying, or injection molding processes, and cured at room temperature to 100 °C for 48 hours to obtain a phosphorous hybrid hyperbranched organosilicon polymer modified polyurethane elastomer material.

[0147] Figure 16 、 17 It can be seen from 17 that the cured polyurethane elastomer self-extinguishes and has no dripping when removed from the flame during the vertical burning test, showing excellent flame retardant performance.

[0148] Example 9

[0149] A preparation method of a highly reactive phosphorous hybrid hyperbranched organosilicon polymer includes the following steps:

[0150] (1) The preparation step of the phosphorous modified silane monomer is as follows: Under the protection of an inert gas, 1 mol of pentaerythritol phosphate, 2 mol of ethyl acetate solvent, 1 mol of glycidyl ether propyltrimethoxysilane, and 0.5 wt% of triethylamine catalyst are added to a three-necked flask equipped with a condenser and mechanical stirrer. After stirring evenly at room temperature, it is slowly heated to 70 °C and reacted for 12 h.

[0151] (2) The purification step of the phosphorous modified silane monomer is as follows: Remove the heating device, naturally cool to 50 °C, and use a thin film evaporator to remove the residual ethyl acetate and triethylamine in the reaction system to obtain a low-viscosity yellow transparent liquid, which is the phosphorous modified silane monomer.

[0152] (3) The preparation step of the phosphorous hybrid hyperbranched organosilicon polymer: Under the protection of an inert gas, 0.01 mol of phosphorous modified silane monomer, 0.99 mol of aminopropyltriethoxysilane, 0.4 mol of phenyltriethoxysilane, 1.3 mol of deionized water, and 3 mol of ethanol solvent are added to a three-necked flask equipped with a condenser and mechanical stirrer. After hydrolysis reaction at room temperature for 1 h, it is slowly heated to 70 °C and reacted for 4 h.

[0153] (4) The purification step of the phosphorous hybrid hyperbranched organosilicon polymer is as follows: Turn off the heating and naturally cool to 50 °C, and use a rotary evaporator to remove the residual ethanol and water in the reaction system to obtain a medium-viscosity yellow transparent liquid, which is the highly reactive phosphorous hybrid hyperbranched organosilicon polymer.

[0154] The room temperature viscosity of the phosphorous hybrid hyperbranched organosilicon polymer prepared in this example is tested. Using a rotary viscometer according to the viscosity measurement method of GB-T 10247-2008, the shear viscosity is 2689 mPa·s.

[0155] Comparative Example 1

[0156] The implementation method of the SFR-100 silicone-based flame retardant modified polyurethane elastomer material is as follows:

[0157] Mix SFR-100 with polyurethane prepolymer and curing agent in a ratio of 0, 10, 20, 30, 40:80:20, mechanically stir at 3000 rpm for 5 minutes under vacuum conditions, perform degassing treatment after ensuring uniform dispersion; then introduce the mixture into the mold through casting, spraying or injection molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the SFR-100 silicone-based flame retardant modified polyurethane elastomer material.

[0158] Figure 18 It can be seen that the compatibility between the flame retardant and the polyurethane material is poor, and there is an obvious phase separation phenomenon after mixing, and the performance drops significantly.

[0159] Comparative Example 2

[0160] The implementation method of the DMMP phosphorus-based flame retardant modified polyurethane elastomer material is as follows:

[0161] Mix DMMP with polyurethane prepolymer and curing agent in a ratio of 0, 10, 20, 30, 40:80:20, mechanically stir at 3000 rpm for 5 minutes under vacuum conditions, perform degassing treatment after ensuring uniform dispersion; then introduce the mixture into the mold through casting, spraying or injection molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the DMMP phosphorus-based flame retardant modified polyurethane elastomer material.

[0162] Figure 19 It can be seen that the addition of DMMP seriously affects the normal curing of the polyurethane material. When the addition amount > 10%, the polyurethane cannot be cured into a film.

[0163] Comparative Example 3

[0164] The implementation method of the TEP phosphorus-based flame retardant modified polyurethane elastomer material is as follows:

[0165] Mix TEP with polyurethane prepolymer and curing agent in a ratio of 0, 10, 20, 30, 40:80:20, mechanically stir at 3000 rpm for 5 minutes under vacuum conditions, perform degassing treatment after ensuring uniform dispersion; then introduce the mixture into the mold through casting, spraying or injection molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the TEP phosphorus-based flame retardant modified polyurethane elastomer material.

[0166] From Figure 20 、 21It can be seen that the chemical resistance of the TEP-modified polyurethane elastomer is poor and the stability is low. It shows a high affinity for both the aqueous phase and the oil phase. It has a high water absorption and oil absorption rate, and there are certain potential hazards during use.

[0167] Comparative Example 4

[0168] The implementation method of the DOPO phosphorus-based flame retardant modified polyurethane elastomer material is as follows:

[0169] Mix DOPO with the polyurethane prepolymer and the curing agent in a ratio of 0, 10, 20, 30, 40:80:20, and mechanically stir at 3000 rpm for 5 minutes under vacuum conditions. After ensuring uniform dispersion, perform degassing treatment; then introduce the mixture into the mold through casting, spraying or injection molding processes, and cure at room temperature to 100 °C for 48 hours to obtain the DOPO phosphorus-based flame retardant modified polyurethane elastomer material.

[0170] Figure 22 、 Figure 23 It can be seen that although the addition of DOPO can improve the flame retardancy of the polyurethane material to a certain extent, it still cannot achieve self-extinguishing after leaving the fire in the face of the hot flow flame burning, and there is a serious dripping phenomenon, and there is no obvious improvement in the ablation resistance and temperature resistance of the material.

Claims

1. A low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer, characterized in that: A hyperbranched organosilicon polymer with a highly branched and non-fully regular three-dimensional network structure is formed by the controlled hydrolysis and condensation of a phosphorus-modified silane monomer and a silane monomer under acidic conditions; the phosphorus-hybridized hyperbranched organosilicon polymer has a Si-O-Si main chain structure and is rich in phosphorus on the side chains.

2. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 1, characterized in that, It includes the following steps: Step 1, mix an alkaline catalyst, a phosphorus source, a silane coupling agent containing a glycidyl ether group with a solvent, react at 30 - 150 °C, and purify to obtain a phosphorus-modified silane monomer; Step 2, mix an acidic catalyst, water, a solvent, a silane monomer and a phosphorus-modified silane monomer, react at 60 - 100 °C, and purify to obtain a low-viscosity intumescent flame-retardant phosphorus-hybridized hyperbranched organosilicon polymer.

3. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: In the said Step 1, the alkaline catalyst is any one of triethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundec-7-ene, 4-dimethylaminopyridine, diethylenetriamine, triethylamine.

4. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: In the said Step 1, the phosphorus source is pentaerythritol phosphate, and the silane coupling agent containing a glycidyl ether group is one or more of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane.

5. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: In the said Step 1, the molar ratio of the phosphorus source, the silane coupling agent containing a glycidyl ether group to the solvent is 1:1:1 - 3, and the addition amount of the alkaline catalyst is 0.1 - 1 wt% of the total mass of the phosphorus source, the silane coupling agent containing a glycidyl ether group and the solvent.

6. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: The molecular structural formula of the phosphorus-modified silane monomer in the said Step 1 is: Among them, R1 is at least one of methyl and ethyl.

7. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: The molecular structural formula of the silane monomer in the said Step 2 is: Among them, R1 is at least one of methyl or ethyl, and R2 is one or more of anilinomethyl, aminopropyl, mercaptopropyl, acryloxypropyl, methyl, phenyl, vinyl, glycidyl ether propyl, chloromethyl.

8. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: In the said Step 2, the molar ratio of the phosphorus-modified silane monomer to the silane monomer is 0.01 - 0.99:0.99 - 0.01, and the molar ratio of the silane monomer to water is 1:0.5 - 2.

9. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, wherein: In the said Step 2, the acidic catalyst is one or more of formic acid, hydrochloric acid, acetic acid, sulfuric acid, nitric acid, phosphoric acid.

10. The preparation method of a low-viscosity intumescent flame-retardant phosphorus hybrid hyperbranched organosilicon polymer according to claim 2, characterized in that: The said solvent is one or more of ethanol, methanol, toluene, xylene, dichloromethane, tetrahydrofuran, ethyl acetate, methyl acetate, acetone, dioxane, carbon tetrachloride.

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