Nitrogen phosphorus silicon compounds, methods of making and flame retardant coatings
Patent Information
- Application Number
- CN202510360177.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-25
- Publication Date
- 2026-09-29
AI Technical Summary
[0005]本发明的目的是为了克服现有的阻燃剂常采用卤素阻燃剂在燃烧时释放大量的有毒烟气，对环境造成较大的破坏；磷系阻燃剂与涂层基体的相互作用不足，添加时会导致材料的力学性能下降问题，提供了一种氮磷硅化合物及其制备方法和阻燃涂层，本发明创造性的提供了一种含有氮磷硅三种阻燃元素的新型阻燃剂，该阻燃剂不含卤素，更加环保；同时由于氮磷硅协同阻燃的机理，具有更好的阻燃效果
[0038](1)本发明提供的新型的氮磷硅化合物可以作为阻燃剂，该氮磷硅化合物不含卤素，相比于传统的含卤阻燃剂来说更加环保。
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Figure CN122832291A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of chemical materials technology, and more particularly to the field of flame retardant materials technology, specifically to a nitrogen-phosphorus-silicon compound, its preparation method, and a flame retardant coating. Background Technology
[0002] Polymer coating materials have attracted widespread attention due to their advantages such as simple application and low cost, and are often used as protective coatings. However, polymer elastomers generally have high flammability, making them difficult to resist flame exposure during use, and their flammability can even cause the fire to spread further.
[0003] To address the flammability of polymer elastomers, the application of flame-retardant compounds in elastomers has become an important method for preparing high-performance products. These flame-retardant materials form an oxide layer on their surface during combustion after thermal degradation, thereby lowering the combustion temperature and blocking oxygen. In practical preparation, flame-retardant materials can be added during or after polymerization, effectively enhancing the flame-retardant properties of the material.
[0004] Halogen compounds generate halogen-containing fumes during the flame retardant process, which pose significant hazards to the environment and human health. Currently, phosphorus-containing flame retardants are commonly used; however, adding phosphorus compounds alone to polymer elastomers can lead to a decrease in the mechanical properties of the material. Summary of the Invention
[0005] The purpose of this invention is to overcome the problems of existing flame retardants, such as the release of large amounts of toxic fumes during combustion, which causes significant environmental damage, and the insufficient interaction between phosphorus-based flame retardants and the coating substrate, which leads to a decrease in the mechanical properties of the material when added. This invention provides a nitrogen-phosphorus-silicon compound, its preparation method, and a flame-retardant coating. This invention creatively provides a novel flame retardant containing three flame-retardant elements: nitrogen, phosphorus, and silicon. This flame retardant is halogen-free and more environmentally friendly. At the same time, due to the synergistic flame-retardant mechanism of nitrogen, phosphorus, and silicon, it has a better flame-retardant effect.
[0006] To achieve the above objectives, the present invention provides a nitrogen-phosphorus-silicon compound, the structure of which is shown in formula (1):
[0007]
[0008] A second aspect of the present invention provides a method for preparing the nitrogen-phosphorus-silicon compound described above, the method comprising: reacting a siloxane compound with a diphenyl halophosphate in the presence of a first catalyst and a first solvent;
[0009] The siloxane compound is octaphenylaminopropyl cage-like polysilsesquioxane;
[0010] The structure of the halophosphate diphenyl ester is shown in formula (2):
[0011] Where X is a halogen, preferably chlorine or bromine.
[0012] Preferably, the weight ratio of the siloxane compound to the diphenyl halophosphate is 1:0.2-2, more preferably 1:1.2-1.5.
[0013] Preferably, the mass ratio of the first catalyst to the siloxane compound is 0.02-0.5:10.
[0014] Preferably, the first catalyst is chloroplatinic acid and / or a cassette catalyst.
[0015] Preferably, the weight ratio of the first solvent to the siloxane compound is 100:5-30, more preferably 100:5-15.
[0016] Preferably, the first solvent is selected from at least one of toluene, xylene, tetrahydrofuran, N,N-dimethylformamide, thionyl chloride, and chloroform.
[0017] Preferably, the reaction conditions include a temperature of 75-85°C and a time of 4-6 hours.
[0018] A third aspect of the present invention provides the application of the aforementioned nitrogen-phosphorus-silicon compounds as flame retardants.
[0019] A fourth aspect of the present invention provides a flame-retardant coating, which is obtained by mixing component A and component B; wherein component A contains a silicon-containing prepolymer and a flame retardant, and component B contains a curing agent and an inorganic filler; the silicon-containing prepolymer is obtained by polymerization of hydroxysiloxane and isocyanate in the presence of a second catalyst; and the flame retardant is the nitrogen-phosphorus-silicon compound described above.
[0020] Preferably, the weight ratio of the hydroxysiloxane to the isocyanate is 0.5-1:1.
[0021] Preferably, the hydroxysiloxane is a hydroxyl-terminated polydimethylsiloxane with a molecular weight of 800-1500 g / mol.
[0022] Preferably, the isocyanate is selected from at least one of isophorone diisocyanate, toluene diisocyanate, and phenylmethane diisocyanate.
[0023] Preferably, the weight ratio of the second catalyst to the hydroxysiloxane is 0.01-0.05:1.
[0024] Preferably, the second catalyst is selected from at least one of dibutyltin dilaurate, triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, and tin naphthenate.
[0025] Preferably, the conditions for the polymerization reaction include: a temperature of 85-95°C and a time of 5-8 hours.
[0026] Preferably, the preparation process of the silicon-containing prepolymer includes: dissolving hydroxysiloxane and isocyanate in a second solvent, then mixing with a second catalyst, and then heating to carry out a polymerization reaction.
[0027] Preferably, the weight ratio of the second solvent to the hydroxysiloxane is 1-3:1.
[0028] Preferably, the second solvent is toluene and / or xylene.
[0029] Preferably, the preparation method of component A includes: mixing the silicon-containing prepolymer reaction liquid obtained by polymerization with a flame retardant, and then removing the second solvent to obtain component A; or,
[0030] The second solvent was removed from the silicon-containing prepolymer reaction liquid obtained by the polymerization reaction, and then it was mixed with the flame retardant to obtain component A.
[0031] Preferably, the amount of the flame retardant is 20-50% by weight of the hydroxysiloxane.
[0032] Preferably, the amount of inorganic filler is 10-20% by weight, based on the total weight of the curing agent and the inorganic filler.
[0033] Preferably, the inorganic filler is at least one selected from bentonite, titanium dioxide, fumed silica, and magnesium hydroxide.
[0034] Preferably, the curing agent includes a first curing agent and a second curing agent, wherein the first curing agent is a polyetheramine curing agent and the second curing agent is tannic acid.
[0035] More preferably, the weight ratio of the first curing agent to the second curing agent is 0.5-2:1.
[0036] Preferably, the weight ratio of component A to component B is 1.5-2.5:1.
[0037] Compared with the prior art, the present invention has at least the following beneficial effects:
[0038] (1) The novel nitrogen-phosphorus-silicon compound provided by the present invention can be used as a flame retardant. The nitrogen-phosphorus-silicon compound does not contain halogens and is more environmentally friendly than traditional halogen-containing flame retardants.
[0039] (2) The nitrogen-phosphorus-silicon compound designed and synthesized in this invention is used as a flame retardant. During combustion, the cage-like silsesquioxane in the nitrogen-phosphorus-silicon flame retardant is oxidized into inorganic silicon dioxide to form a combustion barrier. The nitrogen and phosphorus elements work together to capture free radicals in the gas phase during combustion and block the combustion reaction, thereby achieving the flame retardant effect of the coating.
[0040] (3) The present invention innovatively grafts diphenyl halophosphate onto amino polyhedral oligomeric silsesquioxane to form a compound containing three flame retardant elements: nitrogen, phosphorus, and silicon. This method is simple and easy to operate.
[0041] (4) The nitrogen-phosphorus-silicon compound described in this invention is used to form a coating composed of a flame retardant, a silicon-containing prepolymer, a flame retardant, a curing agent, and inorganic fillers. The resulting coating contains silicon chains, which have good compatibility with the cage-like silsesquioxane in the flame retardant. Therefore, the mechanical properties of the coating are not reduced. Furthermore, the reinforcing effect of the silsesquioxane improves the mechanical properties of the substrate. Using the nitrogen-phosphorus-silicon compound synthesized in this invention as a flame retardant, the oxygen index of the resulting flame-retardant coating can reach 25%, and the mechanical properties of the substrate are improved before and after the addition of the flame retardant. Attached Figure Description
[0042] Figure 1 The image shows the infrared spectrum of the nitrogen-phosphorus-silicon compound prepared in the example.
[0043] Figure 2 The image shows the static tensile test results of the flame-retardant coatings prepared in Example 5, Comparative Example 1, and Comparative Example 2. Detailed Implementation
[0044] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.
[0045] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0046] The structure of the nitrogen-phosphorus-silicon compound provided by this invention is shown in formula (1):
[0047]
[0048] This nitrogen-phosphorus-silicon compound contains all three elements: nitrogen, phosphorus, and silicon, and has a unique structure. It can be used as a novel flame retardant. Compared with traditional halogenated flame retardants, it is not only more environmentally friendly as it is halogen-free, but also has a better flame retardant effect due to its synergistic flame retardant mechanism of nitrogen, phosphorus, and silicon.
[0049] The method for preparing the nitrogen-phosphorus-silicon compound described above, provided by the present invention, includes: reacting a siloxane compound with a halophosphate diphenyl ester in the presence of a first catalyst and a first solvent, wherein the siloxane compound is an octaphenylaminopropyl cage-like polysilsesquioxane.
[0050] The structure of the halophosphate diphenyl ester is shown in formula (2):
[0051] Where X is a halogen.
[0052] This invention creatively grafts diphenyl halophosphate onto a specific amino polyhedral oligomeric silsesquioxane (octaphenylaminopropyl cage-like polysilsesquioxane) to form a novel compound containing three flame-retardant elements: nitrogen, phosphorus, and silicon. The method is simple and easy to operate.
[0053] In this invention, the halogen X in formula (2) can be a conventional choice in the art. In a preferred embodiment, X is chlorine or bromine; more preferably, it is chlorine, i.e., the diphenyl halogenated phosphate is diphenyl chlorophosphate.
[0054] In the method described in this invention, when X in formula (2) is chlorine, the reaction equation for octaphenylaminopropyl cage-like polysilsesquioxane with diphenyl chlorophosphate is as follows:
[0055]
[0056] In a more specific embodiment, the preparation method of the nitrogen-phosphorus-silicon compound includes: mixing a siloxane compound, a first catalyst, and a first solvent; then heating the mixture to 40-50°C under an inert atmosphere and mechanical stirring; subsequently adding a diphenyl halophosphate to the resulting solution; and then heating the mixture to the reaction temperature to carry out the reaction. After the reaction is completed, the solvent and byproducts are removed by rotary evaporation. The inert atmosphere can be a common inert atmosphere or a nitrogen atmosphere.
[0057] In some embodiments, the weight ratio of the siloxane compound to the diphenyl halophosphate can be 1:0.2-2, for example, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5. To reduce the occurrence of side reactions, in some preferred embodiments, the weight ratio of the siloxane compound to the diphenyl halophosphate is 1:1.2-1.5.
[0058] In this invention, the first catalyst can be a conventional choice in the art. In a preferred embodiment, the first catalyst can be chloroplatinic acid and / or a cassette catalyst. In some embodiments, the mass ratio of the first catalyst to the siloxane compound can be 0.02-0.5:10.
[0059] In this invention, the first solvent can be a common organic solvent in the art, as long as it can dissolve the siloxane compound and the diphenyl halophosphate. In some embodiments, the first solvent can be selected from at least one of toluene, xylene, tetrahydrofuran, N,N-dimethylformamide, sulfoxide, and chloroform. In this invention, the amount of the first solvent is not particularly limited, as long as it can ensure that the reaction proceeds normally. In other embodiments, the weight ratio of the first solvent to the siloxane compound can be 100:5-30, preferably 100:5-15.
[0060] In order to react the siloxane compound with the halophosphate diphenyl ester to obtain the product shown in formula (1) and at the same time reduce the occurrence of side reactions, in a preferred embodiment, the reaction temperature is 75-85°C and the reaction time is 4-6 hours.
[0061] This invention uses a simple method to react specific reactants to creatively obtain novel nitrogen, phosphorus, and silicon compounds.
[0062] This invention also provides the application of the aforementioned nitrogen-phosphorus-silicon compound as a flame retardant. When the nitrogen-phosphorus-silicon compound of formula (1) provided by this invention is used as a flame retardant, the cage-like silsesquioxane in the flame retardant is oxidized to inorganic silicon dioxide during combustion, forming a combustion barrier. The nitrogen and phosphorus elements synergistically retard the flame, capturing free radicals in the gas phase during combustion and blocking the combustion reaction, thereby achieving the flame-retardant effect of the coating. This nitrogen-phosphorus-silicon compound has a wide range of applications as a flame retardant and can be used in various flame-retardant coatings and coatings. In a preferred embodiment, the nitrogen-phosphorus-silicon compound of this invention can be used in silicon-containing flame-retardant coatings and coatings.
[0063] This invention also provides a flame-retardant coating, which is obtained by mixing component A and component B. Component A contains a silicon-containing prepolymer and a flame retardant, while component B contains a curing agent and an inorganic filler. Components A and B are stored separately before use to prevent premature contact and curing. The silicon-containing prepolymer is obtained by polymerization of hydroxysiloxane and isocyanate in the presence of a second catalyst; the flame retardant is the nitrogen-phosphorus-silicon compound described above.
[0064] In a preferred embodiment, the preparation process of the silicon-containing prepolymer includes: dissolving hydroxysiloxane and isocyanate in a second solvent, then mixing them with a second catalyst, and then heating to carry out a polymerization reaction. In a more preferred embodiment, the preparation process of the silicon-containing prepolymer includes: adding hydroxysiloxane and isocyanate to a three-necked flask, adding a second solvent while stirring, adding the catalyst after complete dissolution, and heating to the reaction temperature to carry out a polymerization reaction.
[0065] In some embodiments, the weight ratio of the hydroxysiloxane to the isocyanate can be 0.5-1:1, for example, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1:1. In a preferred embodiment, the hydroxysiloxane can be a hydroxyl-terminated polydimethylsiloxane with the structural formula [(CH3)2SiO]. n -(OH)2; more preferably, the molecular weight of the hydroxysiloxane is 800-1500 g / mol. In some embodiments, the isocyanate may be selected from at least one of isophorone diisocyanate, toluene diisocyanate, and phenylmethane diisocyanate.
[0066] In the preparation process of the silicon-containing prepolymer described in this invention, the amount of the second catalyst can be selected according to conventional methods in the art. In some embodiments, the weight ratio of the second catalyst to the hydroxysiloxane can be 0.01-0.05:1. In this invention, the second catalyst can be selected from at least one of dibutyltin dilaurate, triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, and tin naphthenate.
[0067] In this invention, the second solvent can be a common organic solvent in the art, as long as it can solvent hydroxysiloxane and isocyanate. In some embodiments, the second solvent can be toluene and / or xylene. In other embodiments, the weight ratio of the second solvent to the hydroxysiloxane can be 1-3:1.
[0068] In the preparation process of the silicon-containing prepolymer described in this invention, the polymerization temperature can be 85-95°C, and the polymerization time can be 5-8 hours. To obtain the target product while reducing byproducts, in a preferred embodiment, the polymerization temperature is 90°C, and the polymerization time is 6 hours.
[0069] In the flame-retardant coating of this invention, the preparation method of component A is not specifically limited, as long as component A contains a silicon-containing prepolymer and a flame retardant. In one embodiment, the preparation method of component A includes: mixing the silicon-containing prepolymer reaction liquid obtained from the polymerization reaction with a flame retardant, and then removing the second solvent to obtain component A. In another embodiment, the preparation method of component A includes: removing the second solvent from the silicon-containing prepolymer reaction liquid obtained from the polymerization reaction, and then mixing it with a flame retardant to obtain component A. The removal of the second solvent can be carried out by flash evaporation. In this invention, after removing the second solvent, component A also contains a second catalyst and a small amount of hydroxysiloxane and / or isocyanate.
[0070] In a preferred embodiment, the preparation method of component A includes: dissolving hydroxysiloxane and isocyanate in a second solvent, then mixing with a second catalyst, followed by heating to carry out a polymerization reaction, then mixing the silicon-containing prepolymer reaction liquid obtained from the polymerization reaction with a flame retardant, and then removing the second solvent to obtain component A.
[0071] In another preferred embodiment, the preparation method of component A includes: dissolving hydroxysiloxane and isocyanate in a second solvent, then mixing with a second catalyst, then heating to carry out a polymerization reaction, then removing the second solvent from the silicon-containing prepolymer reaction liquid obtained from the polymerization reaction, and then mixing with a flame retardant to obtain component A.
[0072] In the method described in this invention, in order to further improve the flame retardant performance of the coating prepared by the silicon-containing flame retardant coating and to improve the mechanical properties of the material to a certain extent, preferably, the amount of the flame retardant can be 20-50% by weight of component A.
[0073] In the flame-retardant coating of the present invention, the preparation process of component B includes mixing a curing agent and an inorganic filler. In some embodiments, the curing agent and the inorganic filler can be mixed in advance; alternatively, the curing agent and the inorganic filler can be stored separately and mixed only when needed.
[0074] In some embodiments, the amount of inorganic filler can be 10-20% by weight, based on the total weight of the curing agent and the inorganic filler; in some embodiments, the inorganic filler can be at least one of bentonite, titanium dioxide, fumed silica and magnesium hydroxide.
[0075] In a preferred embodiment, to further improve the curing effect of the curing agent, the curing agent includes a first curing agent and a second curing agent. The first curing agent can be a polyetheramine curing agent, and the second curing agent can be tannic acid. The polyetheramine curing agent can be at least one of polyetheramine curing agents T403, D230, and D2000. In some more preferred embodiments, the weight ratio of the first curing agent to the second curing agent can be 0.5-2:1.
[0076] In a preferred embodiment, when the curing agent includes a first curing agent and a second curing agent, the preparation process of component B includes: adding the first curing agent and the second curing agent to a high-speed mixer, then adding inorganic filler, and stirring at 1000-1500 rpm for 20-40 minutes.
[0077] In this invention, a flame-retardant coating is obtained by mixing and curing component A and component B. This flame-retardant coating consists of a matrix and a flame retardant; that is, the matrix is composed of all components except the flame retardant. The coating is formed during the mixing of component A and component B. The mixing conditions for component A and component B include: a temperature of room temperature (15-35°C) and a time of 2-5 minutes.
[0078] In some embodiments, the weight ratio of component A to component B can be 1.5-2.5:1. In a preferred embodiment, the weight ratio of component A to component B is 2:1.
[0079] When the nitrogen-phosphorus-silicon compound described in this invention is used to form a coating with a flame retardant, a silicon-containing prepolymer, a flame retardant, a curing agent, and inorganic fillers, the resulting coating contains silicon chains, which have good compatibility with the cage-like silsesquioxane in the flame retardant, thus not reducing the mechanical properties of the coating. Using the nitrogen-phosphorus-silicon compound synthesized in this invention as a flame retardant, the oxygen index of the resulting flame-retardant coating can reach 25%, and the mechanical properties are improved to some extent after the addition of the flame retardant.
[0080] The following examples further illustrate the nitrogen-phosphorus-silicon compound, its preparation method, and the flame-retardant coating of the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.
[0081] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.
[0082] In the following embodiments:
[0083] The structural formula of hydroxyl-terminated polydimethylsiloxane is [(CH3)2SiO]. n -(OH)2, with a molecular weight of 2000 g / mol, was purchased from Inokai Reagent Company.
[0084] The Castel catalyst was purchased from Aladdin Reagents.
[0085] Example 1
[0086] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0087] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene, and 0.05g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 20g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0088] After infrared spectroscopy characterization, such as Figure 1 As shown, the final product obtained is the nitrogen-phosphorus-silicon compound represented by formula (1).
[0089] (2) Preparation process of flame-retardant coating:
[0090] Preparation of Component A: Add 40g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 50g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 10g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0091] Preparation of Component B: Add 45g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 45g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1500rpm for 30 minutes, and then discharge and package.
[0092] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0093] Example 2
[0094] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0095] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene, and 0.05g of caster catalyst were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 20g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0096] (2) Preparation process of flame-retardant coating:
[0097] Preparation of Component A: 42g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 48g of isophorone diisocyanate were added to a three-necked flask. 100g of xylene was added with stirring. After complete dissolution, 0.7g of dibutyltin dilaurate was added. The mixture was heated to 90℃ and reacted for 6 hours. After cooling to room temperature, 12g of nitrogen-phosphorus-silicon compound was added to the reaction solution and stirred thoroughly. The solvent was removed by rotary evaporation and the product was discharged and packaged.
[0098] Preparation of component B: Add 40g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 50g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1000rpm for 30 minutes, and then discharge and package.
[0099] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0100] Example 3
[0101] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0102] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene, and 0.08g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 20g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0103] (2) Preparation process of flame-retardant coating:
[0104] Preparation of Component A: Add 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.7g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 15g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0105] Preparation of component B: Add 37g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 53g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1000rpm for 30 minutes, and then discharge and package.
[0106] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0107] Example 4
[0108] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0109] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene and 0.1g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 20g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0110] (2) Preparation process of flame-retardant coating:
[0111] Preparation of Component A: 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate were added to a three-necked flask. 100g of xylene was added with stirring. After complete dissolution, 0.6g of dibutyltin dilaurate was added. The mixture was heated to 90℃ and reacted for 6 hours. After cooling to room temperature, 18g of nitrogen-phosphorus-silicon compound was added to the reaction solution and stirred thoroughly. The solvent was removed by rotary evaporation and the product was discharged and packaged.
[0112] Preparation of component B: Add 32g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 58g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1000rpm for 30 minutes, and then discharge and package.
[0113] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0114] Example 5
[0115] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0116] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene and 0.1g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 20g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0117] (2) Preparation process of flame-retardant coating:
[0118] Preparation of Component A: Add 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 20g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0119] Preparation of component B: Add 30g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 60g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1500rpm for 30 minutes, and then discharge and package.
[0120] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0121] Example 6
[0122] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0123] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene, and 0.1g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 18g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0124] (2) Preparation process of flame-retardant coating:
[0125] Preparation of Component A: Add 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.7g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 20g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0126] Preparation of component B: Add 30g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 60g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1000rpm for 30 minutes, and then discharge and package.
[0127] (3) Preparation process of flame retardant coating:
[0128] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0129] Example 7
[0130] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0131] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene and 0.1g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 16g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0132] (2) Preparation process of flame-retardant coating:
[0133] Preparation of Component A: Add 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 20g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0134] Preparation of component B: Add 30g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 60g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1500rpm for 30 minutes, and then discharge and package.
[0135] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0136] Example 8
[0137] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0138] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene, and 0.1g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 14g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0139] (2) Preparation process of flame-retardant coating:
[0140] Preparation of Component A: Add 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 20g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0141] Preparation of component B: Add 30g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 60g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1000rpm for 30 minutes, and then discharge and package.
[0142] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0143] Example 9
[0144] (1) Preparation process of nitrogen, phosphorus and silicon compounds:
[0145] 10g of octaphenylaminopropyl cage-like polysilsesquioxane, 100g of xylene, and 0.1g of chloroplatinic acid were sequentially added to a four-necked flask. The mixture was heated to 45°C under a nitrogen atmosphere and with mechanical stirring. Then, 12g of diphenyl chlorophosphate was added to the above solution, and the mixture was heated to 80°C and reacted for 4 hours. The solvent and byproducts were removed by rotary evaporation to obtain the final product.
[0146] (2) Preparation process of flame-retardant coating:
[0147] Preparation of Component A: Add 45g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 45g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 20g of nitrogen-phosphorus-silicon compound to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0148] Preparation of component B: Add 30g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 60g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1500rpm for 30 minutes, and then discharge and package.
[0149] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0150] Comparative Example 1
[0151] The method of Example 1 was followed, except that ammonium polyphosphate flame retardant (purchased from Maclean's Reagent Company, molecular weight 1000 g / mol) was used instead of nitrogen-phosphorus-silicon compounds.
[0152] Preparation process of flame retardant coating:
[0153] Preparation of Component A: Add 40g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 50g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, add 10g of ammonium polyphosphate flame retardant to the reaction solution, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0154] Preparation of Component B: Add 45g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 45g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1500rpm for 30 minutes, and then discharge and package.
[0155] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0156] Comparative Example 2
[0157] The method described in Example 1 was implemented, except that no flame retardant was added.
[0158] Preparation process of flame retardant coating:
[0159] Preparation of Component A: Add 40g of hydroxyl-terminated polydimethylsiloxane (molecular weight 2000g / mol) and 50g of isophorone diisocyanate to a three-necked flask, add 100g of xylene while stirring, and after it is fully dissolved, add 0.6g of dibutyltin dilaurate, heat to 90℃ and react for 6 hours, let stand and cool to room temperature, stir and mix thoroughly, remove the solvent by rotary evaporation, and then discharge and package.
[0160] Preparation of Component B: Add 45g of polyetheramine D230 (purchased from Huntsman, molecular weight 230g / mol) and 45g of tannic acid to a high-speed mixer, then add 10g of inorganic filler (fumed silica), stir at 1500rpm for 30 minutes, and then discharge and package.
[0161] Mix components A and B at a weight ratio of 2:1 at room temperature (25℃) for 3 minutes.
[0162] Test Example 1
[0163] The flame-retardant coatings prepared in the examples and comparative examples were tested for oxygen index, and the results are shown in Table 1. The oxygen content in the air is 21%, and only materials with an oxygen index greater than this value exhibit flame retardancy.
[0164] The oxygen index test method is as follows: Set the oxygen concentration, install the sample vertically at the center of the combustion chamber, ignite the sample, observe the combustion phenomenon, and record the duration of combustion or the distance burned. Adjust the oxygen concentration until the combustion time of the sample is less than 180 seconds or the combustion distance is less than 50 mm, and record the oxygen concentration at this point as the oxygen index.
[0165] Table 1
[0166]
[0167]
[0168] As can be seen from Table 1, the flame-retardant coating prepared by the method described in this invention has a high oxygen index and excellent flame-retardant properties.
[0169] Test Example 2
[0170] The mechanical properties of the flame-retardant coatings prepared in the examples and comparative examples were tested, and the results are shown in Table 2. The static tensile test results of the flame-retardant coatings prepared in Example 5, Comparative Example 1, and Comparative Example 2 are shown in the figure below. Figure 2 As shown.
[0171] Mechanical properties were tested using a universal tensile testing machine. The samples were cut into dumbbell shapes with a 4mm width at the narrow neck, and the thickness was measured using vernier calipers. Tensile strength was calculated as the ratio of maximum load to cross-sectional area, and elongation at break was calculated as the ratio of maximum clamp displacement to clamp spacing. The clamp spacing was 40mm, and the tensile speed was 100mm / min.
[0172] Table 2
[0173]
[0174]
[0175] As can be seen from Table 2, the mechanical properties of the flame-retardant coating prepared by the method described in this invention are significantly improved.
[0176] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A nitrogen-phosphorus-silicon compound, characterized in that, The structure of this nitrogen-phosphorus-silicon compound is shown in formula (1):
2. A method for preparing the nitrogen-phosphorus-silicon compound of claim 1, characterized in that, The method includes reacting a siloxane compound with a halophosphate diphenyl ester in the presence of a first catalyst and a first solvent; The siloxane compound is octaphenylaminopropyl cage-like polysilsesquioxane; The structure of the halophosphate diphenyl ester is shown in formula (2): Where X is a halogen, preferably chlorine or bromine.
3. The method according to claim 2, characterized in that, The weight ratio of the siloxane compound to the diphenyl halophosphate is 1:0.2-2, preferably 1:1.2-1.
5.
4. The method according to claim 2 or 3, characterized in that, The mass ratio of the first catalyst to the siloxane compound is 0.02-0.5:10; Preferably, the first catalyst is chloroplatinic acid and / or a cassette catalyst.
5. The method according to any one of claims 2-4, characterized in that, The weight ratio of the first solvent to the siloxane compound is 100:5-30, preferably 100:5-15; Preferably, the first solvent is selected from at least one of toluene, xylene, tetrahydrofuran, N,N-dimethylformamide, thionyl chloride, and chloroform.
6. The method according to any one of claims 2-4, characterized in that, The reaction conditions include a temperature of 75-85°C and a time of 4-6 hours.
7. The use of the nitrogen-phosphorus-silicon compound of claim 1 as a flame retardant.
8. A flame-retardant coating, characterized in that, The flame-retardant coating is obtained by mixing component A and component B; Component A contains a silicon-containing prepolymer and a flame retardant, while component B contains a curing agent and an inorganic filler. The silicon-containing prepolymer is obtained by polymerization of hydroxysiloxane and isocyanate in the presence of a second catalyst. The flame retardant is the nitrogen-phosphorus-silicon compound as described in claim 1.
9. The flame-retardant coating according to claim 8, characterized in that, The weight ratio of the hydroxysiloxane to the isocyanate is 0.5-1:1; Preferably, the hydroxysiloxane is a hydroxyl-terminated polydimethylsiloxane with a molecular weight of 800-1500 g / mol; Preferably, the isocyanate is selected from at least one of isophorone diisocyanate, toluene diisocyanate, and phenylmethane diisocyanate.
10. The flame-retardant coating according to claim 8 or 9, characterized in that, The weight ratio of the second catalyst to the hydroxysiloxane is 0.01-0.05:1; Preferably, the second catalyst is selected from at least one of dibutyltin dilaurate, triethylenediamine, bis(dimethylaminoethyl) ether, stannous octoate, and tin naphthenate.
11. The flame-retardant coating according to any one of claims 8-10, characterized in that, The polymerization reaction conditions include a temperature of 85-95°C and a time of 5-8 hours.
12. The flame-retardant coating according to any one of claims 8-11, characterized in that, The preparation process of the silicon-containing prepolymer includes: dissolving hydroxysiloxane and isocyanate in a second solvent, then mixing with a second catalyst, and then heating to carry out a polymerization reaction; Preferably, the weight ratio of the second solvent to the hydroxysiloxane is 1-3:1; Preferably, the second solvent is toluene and / or xylene.
13. The flame-retardant coating according to claim 12, characterized in that, The preparation method of component A includes: mixing the silicon-containing prepolymer reaction liquid obtained by polymerization with a flame retardant, and then removing the second solvent to obtain component A; or, The second solvent was removed from the silicon-containing prepolymer reaction liquid obtained by the polymerization reaction, and then it was mixed with the flame retardant to obtain component A; Preferably, the amount of the flame retardant is 20-50% by weight of the hydroxysiloxane.
14. The flame-retardant coating according to any one of claims 8-13, characterized in that, Based on the total weight of the curing agent and the inorganic filler, the amount of the inorganic filler is 10-20% by weight; Preferably, the inorganic filler is at least one selected from bentonite, titanium dioxide, fumed silica, and magnesium hydroxide; Preferably, the curing agent includes a first curing agent and a second curing agent, wherein the first curing agent is a polyetheramine curing agent and the second curing agent is tannic acid; More preferably, the weight ratio of the first curing agent to the second curing agent is 0.5-2:
1.
15. The flame-retardant coating according to any one of claims 8-14, characterized in that, The weight ratio of component A to component B is 1.5-2.5:1.