Silicon-phosphorus flame retardant, preparation method, fireproof coating and application

Abstract

The invention relates to the technical field of flame-retardant materials, in particular to a silicon-phosphorus flame retardant, a preparation method, a fireproof coating and application. The silicon-phosphorus flame retardant contains a compound with a structure as shown in a formula (1), the silicon-phosphorus flame retardant is used for preparing the fireproof coating, the thickness of a carbon layer of the fireproof coating can reach 33 mm or above, and meanwhile, the fireproof time can reach 180 min or above;

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flame-retardant materials, in particular to a silicon-phosphorus flame retardant, a preparation method thereof, a fireproof coating and application. BACKGROUND

[0002] Petroleum chemical enterprises are high-risk industries, and fire safety has always been an important challenge for enterprises. Intumescent fireproof coating is a new type of fireproof material, which can form a foam-like protective layer at high temperatures, effectively isolating the fire source and preventing the spread of fire. This fireproof coating has the advantages of thin coating, strong adhesion, good fireproof performance, easy construction, and aesthetic appearance. It can be painted on the surface of buildings and equipment to form a fireproof protective layer, effectively isolating the fire source and preventing the spread of fire, and has been widely used in petroleum chemical enterprises.

[0003] According to the characteristics of intumescent fireproof coating, this fireproof coating needs to form an expanded carbon layer to isolate the flame when exposed to fire, therefore, the performance of the expanded carbon layer has an important influence on the fire resistance time of this fireproof coating. In recent years, research institutions and enterprises at home and abroad have been actively developing intumescent fireproof coating. CN111234564B discloses an environmentally friendly flame retardant and a preparation method of fireproof coating thereof, which is prepared by stripping zirconium phosphate with tetrabutylammonium hydroxide and phosphoric acid, and then coating the zirconium phosphate with furfurylamine. The fire resistance time of this fireproof coating can reach 130 minutes, but the carbon layer thickness of this fireproof coating is only 18.6mm, and the fireproof performance of the thin carbon layer is limited. CN111349355B discloses a modified ammonium polyphosphate for improving the flame retardant performance of fireproof coating and a preparation method of fireproof coating thereof. The carbon layer thickness of this fireproof coating is even thinner, and the fire resistance time is not more than 120 minutes. CN113831597A discloses a bio-based macromolecule modified nano-zirconium phosphate flame retardant and fireproof coating thereof. The fire resistance time of this fireproof coating can reach 168 minutes, but the maximum carbon layer thickness is only 15.3mm. At present, the carbon layer of this intumescent fireproof coating is generally thin, the carbon layer performance is not clear, and the fire resistance time is short. SUMMARY

[0004] The present application aims to solve the problems of thin carbon layer, unclear carbon layer performance and short fire resistance time of intumescent fireproof coating in the prior art, and provides a silicon-phosphorus flame retardant, a preparation method thereof, a fireproof coating and application. The silicon-phosphorus flame retardant contains a compound with a special structure, and the use of the silicon-phosphorus flame retardant in the preparation of fireproof coating can make the carbon layer thickness of the fireproof coating reach more than 33mm, and the fire resistance time can reach more than 180 minutes.

[0005] To achieve the above object, the present application provides a silicon-phosphorus flame retardant containing a compound having a structure shown in formula (1),

[0006]

[0007] wherein R1 is hydrogen, C1-C3 alkyl or tetraethyl phosphate group, and R2 is C1-C5 alkyl.

[0008] Preferably, R1 is hydrogen, methyl or tetraethyl phosphate group, and R2 is methyl, ethyl or butyl.

[0009] The present application provides a method for preparing a silicon-phosphorus flame retardant, which comprises the following steps:

[0010] (1) mixing and reacting unsaturated phosphate ester, solvent, catalyst and polysiloxane;

[0011] (2) performing solid-liquid separation on the reaction product obtained in step (1), and drying the solid phase part; wherein the catalyst is chloroplatinic acid and / or Karstedt catalyst.

[0012] Preferably, the unsaturated phosphate ester is a compound having a structure shown in formula (2) and / or a compound having a structure shown in formula (3),

[0013]

[0014] wherein R3 and R4 are each independently selected from methyl, ethyl, butyl and vinyl, and R5 is vinyl, methoxy or propenyl; R6, R7, R8 and R9 are each independently selected from ethyl, methyl and propyl.

[0015] More preferably, the unsaturated phosphate ester is selected from one or two or more of vinyl phosphonic diethyl ester, vinyl-1,1-tetraethyl diphosphate, dimethyl-vinyl phosphonate and dibutyl allyl phosphonate.

[0016] Preferably, the polysiloxane is cage polysilsesquioxane.

[0017] Preferably, the solvent is selected from one or two or more of toluene, xylene, chloroform, N,N-dimethylformamide and dichlorosulfoxide.

[0018] Preferably, the weight ratio of the amount of the unsaturated phosphate ester to the amount of the polysiloxane is 1.25-3:3, more preferably 2-2.5:1.

[0019] Preferably, the weight ratio of the amount of the catalyst to the amount of the unsaturated phosphate ester is 0.5-2:100, more preferably 1-1.5:100.

[0020] Preferably, the weight ratio of the total weight of the unsaturated phosphate and the polysiloxane to the weight of the solvent is 8-15:100.

[0021] Preferably, in step (1), the reaction conditions include: temperature is 60-80℃, time is 3-8h.

[0022] The third aspect of the present application provides a fireproof coating, which contains component A and component B, wherein the component A contains epoxy resin, polyol, first silane coupling agent and silicon-phosphorus flame retardant, the component B contains curing agent, inorganic filler, organic amine and second silane coupling agent; the silicon-phosphorus flame retardant is the silicon-phosphorus flame retardant described above or the silicon-phosphorus flame retardant prepared by the method described above.

[0023] Preferably, the content of the silicon-phosphorus flame retardant is 10-50wt%, the content of the polyol is 5-25wt%, the content of the epoxy resin is 30-60wt%, and the content of the first silane coupling agent is 5-25wt%, based on 100wt% of the total weight of the component A.

[0024] Preferably, the content of the curing agent is 10-40wt%, the content of the inorganic filler is 5-40wt%, the content of the organic amine is 10-40wt%, and the content of the second silane coupling agent is 10-40wt%, based on 100wt% of the total weight of the component B.

[0025] Preferably, the epoxy resin is selected from one or two or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, acrylic modified epoxy resin, silicone modified epoxy resin, polyurethane modified epoxy resin and phenolic modified epoxy resin.

[0026] Preferably, the polyol is selected from one or two or more of pentaerythritol, di-pentaerythritol and amylopectin.

[0027] Preferably, the curing agent is selected from one or two or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0028] Preferably, the inorganic filler is selected from one or two or more of titanium white powder, fumed silica and aerogel powder.

[0029] Preferably, the organic amine is selected from one or two or more of melamine, urea and triazine.

[0030] Preferably, the first silane coupling agent and the second silane coupling agent are each independently selected from one or two or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0031] Preferably, the component A is obtained by mixing the epoxy resin, the polyol, the first silane coupling agent and the silicon-phosphorus flame retardant at 30-50℃; and the component B is obtained by mixing the curing agent, the inorganic filler, the organic amine and the second silane coupling agent at 30-50℃.

[0032] The fourth aspect of the present application provides an application of the fireproof coating described above, which comprises mixing the component A and the component B of the fireproof coating described above, and then coating the obtained mixture on the surface of a building or equipment.

[0033] Preferably, the weight ratio of the amount of the component A to the amount of the component B is 1-4:1.

[0034] Preferably, the coating is performed by spraying, brushing or rolling.

[0035] By the above technical solution, the silicon-phosphorus flame retardant and the preparation method thereof, the fireproof coating and the preparation method and application thereof provided by the present application have at least the following beneficial effects:

[0036] (1) In the present application, the unsaturated phosphate ester with a specific structure is reacted with polysiloxane under the action of a specific catalyst to obtain a silicon-phosphorus flame retardant containing no halogen and having a high content of phosphorus element. The silicon-phosphorus flame retardant can catalyze the dehydration of polymers during combustion, increase the thickness of the carbon layer to more than 33 mm, and prolong the overall fire resistance time of the coating to about 180 min.

[0037] (2) In the preferred case, by adjusting the ratio of the unsaturated phosphate ester, polysiloxane and catalyst and controlling the reaction conditions within a certain range, the silicon-phosphorus flame retardant prepared has a carbon layer with a microporous structure, a low overall thermal conductivity of 0.032 W / m.K, and can well insulate the flame temperature. At the same time, the carbon layer has a compressive strength of 100 kPa, which can effectively prevent the collapse and damage of the carbon layer. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The infrared spectrum of the silicon-phosphorus flame retardant prepared in Example 1;

[0039] Figure 2 The digital photo of the number of carbon layers of the fireproof coating prepared in Example 1;

[0040] Figure 3 The carbon layer compressive strength-displacement graph of the fireproof coating prepared in Example 1 and Comparative Example 2. DETAILED DESCRIPTION

[0041] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and explanatory and are not intended to limit the present application.

[0042] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and values are provided as approximate descriptions of the ranges and values. The endpoints of the ranges of values stated are not to be understood as being limited to the precise values recited as endpoints, but rather are meant to be merely approximate. For numeric values, the endpoints of the ranges of values, the endpoints of the ranges of values and individual point values, and individual point values can be combined with one another to generate one or more new numeric ranges, which are to be considered as being specifically disclosed herein.

[0043] The first aspect of the present application provides a silicon-phosphorus flame retardant, which contains a compound having a structure shown in formula (1),

[0044]

[0045] In the silicon-phosphorus flame retardant described in the present application, in a specific embodiment, R1 is hydrogen, C1-C3 alkyl or tetraethyl phosphate group, and R2 is C1-C5 alkyl. In a preferred embodiment, R1 is hydrogen, methyl or tetraethyl phosphate group, and R2 is methyl, ethyl or butyl. In order to make the carbon layer thickness of the fireproof coating prepared by using the silicon-phosphorus flame retardant to be 40 mm or more, the fire resistance time to be about 180 min, and in order to make the overall thermal conductivity of the fireproof coating to be as low as 0.04 W / m.K and the carbon layer compressive strength to be 100 kPa, in a more preferred embodiment, R1 is methyl, and R2 is ethyl.

[0046] The second aspect of the present application provides a method for preparing the silicon-phosphorus flame retardant described above, which comprises the following steps:

[0047] (1) mixing and reacting unsaturated phosphate, solvent, catalyst and polysiloxane;

[0048] (2) performing solid-liquid separation on the reaction product obtained in step (1), and drying the solid phase part; wherein the catalyst is chloroplatinic acid and / or Karstedt catalyst.

[0049] In the method for preparing the silicon-phosphorus flame retardant described in the present application, in a specific embodiment, the unsaturated phosphate is a compound having a structure shown in formula (2) and / or a compound having a structure shown in formula (3),

[0050]

[0051] wherein R3 and R4 are each independently selected from methyl, ethyl, butyl and vinyl, and R5 is vinyl, methoxy or propenyl; R6, R7, R8 and R9 are each independently selected from ethyl, methyl and propyl.

[0052] In order to make the prepared silicon-phosphorus flame retardant to be used in the preparation of fireproof coating, the carbon layer thickness of the fireproof coating can reach 40mm or more, and the fire resistance time can reach about 180min, in the preferred embodiment, the unsaturated phosphoric acid ester is selected from one or more than two of vinyl phosphoric acid diethyl ester, vinyl-1,1-tetraethyl diphosphate, dimethyl-vinyl phosphoric acid ester and dibutyl allyl phosphonic acid ester.

[0053] In the preparation method of the silicon-phosphorus flame retardant, in the specific embodiment, the solvent can be an organic solvent commonly selected in the art as long as it can dissolve the raw materials. In the preferred embodiment, the solvent is selected from one or more than two of toluene, xylene, trichloromethane, N,N-dimethylformamide and dichlorosulfoxide.

[0054] In the preparation method of the silicon-phosphorus flame retardant, in the specific embodiment, the catalyst is chloroplatinic acid and / or Karstedt catalyst, and specifically, in order to make the catalyst better dissolved, the catalyst is dissolved in isopropanol solution. In the preferred embodiment, the catalyst is dissolved in isopropanol solution, and the concentration of the catalyst is 0.01-0.1mol%.

[0055] In the preparation method of the silicon-phosphorus flame retardant, in the specific embodiment, the Karstedt catalyst can be commonly selected in the art.

[0056] In the more preferred embodiment, the catalyst is chloroplatinic acid.

[0057] In the preparation method of the silicon-phosphorus flame retardant, in the preferred embodiment, the polysiloxane is dimethylsiloxy cage polysilsesquioxane.

[0058] In the preparation method of the silicon-phosphorus flame retardant, in the specific operation process, the unsaturated phosphoric acid ester, the solvent and the catalyst are mixed to obtain a mixed product, and then the polysiloxane is added to the mixed product for reaction. In the preferred case, the reaction conditions include: temperature is 60-80℃, for example, 60℃, 70℃ or 80℃, and time is 3-8h, for example, 3h, 4h, 5h, 6h, 7h or 8h.

[0059] In the preferred case, the mixing is carried out under stirring in an inert atmosphere; more preferably, the mixing conditions include: temperature is 60-80℃, for example, 60℃, 70℃ or 80℃, and time is 1-2h, for example, 1h, 1.5h or 2h.

[0060] In the preparation method of the silicon-phosphorus flame retardant, in specific embodiments, in step (2), the solid-liquid separation can be a conventional selection in the art, and specifically, for example, can be suction filtration, as long as the solvent in the reaction product obtained in step (1) can be removed.

[0061] In the preparation method of the silicon-phosphorus flame retardant, in specific embodiments, in step (2), the drying conditions include: the temperature is 60-80℃, for example, can be 60℃, 70℃ or 80℃, and the time is 24-48h, for example, can be 24h, 30h, 36h, 42h or 48h.

[0062] In specific operations, the dried product is further ground to obtain the silicon-phosphorus flame retardant.

[0063] The third aspect of the present application provides a fireproof coating, which contains component A and component B, and the component A and the component B are stored separately, wherein the component A contains epoxy resin, polyol, first silane coupling agent and silicon-phosphorus flame retardant, the component B contains curing agent, inorganic filler, organic amine and second silane coupling agent; the silicon-phosphorus flame retardant is the silicon-phosphorus flame retardant described above, or the silicon-phosphorus flame retardant prepared by the method described above. The first silane coupling agent and the second silane coupling agent are the same or different.

[0064] In the fireproof coating, in specific embodiments, based on 100wt% of the total weight of the component A, the content of the silicon-phosphorus flame retardant is 10-50wt%, for example, can be 10wt%, 20wt%, 25wt%, 30wt%, 40wt% or 50wt%, the content of the polyol is 5-25wt%, for example, can be 5wt%, 10wt%, 13wt%, 14wt%, 15wt%, 16wt%, 20wt% or 25wt%, the content of the epoxy resin is 30-60wt%, for example, can be 30wt%, 40wt%, 45wt%, 50wt% or 60wt%, and the content of the first silane coupling agent is 5-25wt%, for example, can be 5wt%, 10wt%, 11wt%, 14wt%, 15wt%, 17wt%, 20wt% or 25wt%.

[0065] In order to make the prepared fireproof coating to meet the carbon layer thickness of 40mm or more, the fire resistance time of about 180min, and also can make the overall thermal conductivity to reduce to 0.04W / m.K, the carbon layer compressive strength can reach 100kPa, in the preferred embodiment, the content of the silicon phosphorus flame retardant is 20-30wt% based on the total weight of the component A is 100wt%, the content of the polyol is 10-20wt%, the content of the epoxy resin is 40-50wt%, the content of the first silane coupling agent is 10-20wt%.

[0066] In the fireproof coating of the present application, in the specific embodiment, the content of the curing agent is 10-40wt% based on the total weight of the component B is 100wt%, for example, can be 10wt%, 12.5wt%, 14.3wt%, 18.2wt%, 23.1wt%, 25wt%, 31wt%, 36.4wt% or 40wt%, the content of the inorganic filler is 5-40wt%, for example, can be 5wt%, 9wt%, 16.7wt%, 22.7wt%, 23.1wt%, 25wt%, 25.9wt%, 28.6wt% or 40wt%, the content of the organic amine is 10-40wt%, for example, can be 10wt%, 15.4wt%, 17.2wt%, 22.8wt%, 23wt%, 25wt%, 28.6wt%, 36.4wt% or 40wt%, the content of the second silane coupling agent is 10-40wt%, for example, can be 10wt%, 18.2wt%, 25.9wt%, 28.5wt%, 30.8wt%, 33.3wt%, 36.3wt%, 37.5wt% or 40wt%.

[0067] In the preferred embodiment, the content of the curing agent is 15-35wt% based on the total weight of the component B is 100wt%, the content of the inorganic filler is 15-30wt%, the content of the organic amine is 15-25wt%, the content of the second silane coupling agent is 25-35wt%.

[0068] In the fireproof coating of the present application, in the specific embodiment, the epoxy resin can be the conventional selection in the art. In the preferred embodiment, the epoxy resin is selected from one or two or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, acrylic modified epoxy resin, silicone modified epoxy resin, polyurethane modified epoxy resin and phenolic modified epoxy resin.

[0069] In the fireproof coating of the present application, in specific embodiments, the polyol can be a routine selection in the art. In preferred embodiments, the polyol is selected from one or more of pentaerythritol, dipentaerythritol and amylopectin, more preferably pentaerythritol.

[0070] In the fireproof coating of the present application, in specific embodiments, the curing agent can be a routine selection in the art. In preferred embodiments, the curing agent is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0071] In the fireproof coating of the present application, in specific embodiments, the inorganic filler can be a routine selection in the art. In preferred embodiments, the inorganic filler is selected from one or more of titanium dioxide, fumed silica and aerogel powder.

[0072] In the fireproof coating of the present application, in specific embodiments, the organic amine can be a routine selection in the art. In preferred embodiments, the organic amine is selected from one or more of melamine, urea and triazine.

[0073] In the fireproof coating of the present application, in specific embodiments, both the first silane coupling agent and the second silane coupling agent can be a routine selection in the art. In preferred embodiments, the first silane coupling agent and the second silane coupling agent are each independently selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0074] In specific embodiments, the component A is obtained by mixing the epoxy resin, the polyol, the first silane coupling agent and the silicon-phosphorus flame retardant at 30-50°C;

[0075] The component B is obtained by mixing the curing agent, the inorganic filler, the organic amine and the second silane coupling agent at 30-50°C.

[0076] In specific operations, in preparing the component A as described above, the epoxy resin is first placed in a high-speed disperser, warmed to 30-50°C, stirred at a speed of 500-1500 rpm for 0.5-2 h, the polyol and the first silane coupling agent are added, stirring is continued for 1-3 h, then the silicon-phosphorus flame retardant is added and stirring is continued for 0.5-1.5 h.

[0077] In the specific operation process, when preparing the component B described above, the curing agent is first placed in a high-speed dispersion machine, heated to 30-50℃, stirred at a speed of 500-1500 rpm for 0.5-2 h, then the inorganic filler, the organic amine and the second silane coupling agent are added, and the stirring is continued for 1-3 h.

[0078] The fourth aspect of the present application provides an application of the fireproof coating described above, which comprises mixing the component A and the component B in the fireproof coating, and then coating the obtained mixture on the surface of a building or equipment.

[0079] In the application of the present application, in the specific embodiment, the weight ratio of the amount of the component A to the component B is 1-4:1. In the preferred embodiment, the weight ratio of the amount of the component A to the component B is 1:1.

[0080] In the application of the present application, in the specific embodiment, the coating is performed by spraying, brushing or rolling.

[0081] The present application will be described in detail by way of examples below, but the scope of protection of the present application is not limited to this.

[0082] Unless otherwise specified, the reagents involved in the examples and comparative examples of the present application are all commercially available products.

[0083] 0.03 mol% chloroplatinic acid isopropanol solution: manufacturer: Micell;

[0084] 0.03 mol% Karsted isopropanol solution: manufacturer: Micell;

[0085] Dimethylsiloxy cage polysilsesquioxane: manufacturer: Guangzhou Yixin Technology Co., Ltd., brand: 1015;

[0086] Bisphenol A type epoxy resin: manufacturer: Zhonghua Xingchen Synthetic Material Co., Ltd., brand: E44;

[0087] 3-aminopropyltriethoxysilane: manufacturer: Aldrich Chemical Reagent Co., Ltd.;

[0088] Bisphenol F type epoxy resin: manufacturer: Dow Chemical Company, brand: 351;

[0089] 3-aminopropyltrimethoxysilane: manufacturer: Aldrich Chemical Reagent Co., Ltd.;

[0090] Acrylic modified epoxy resin: manufacturer: Dow Chemical Company, brand: 6330;

[0091] 3-(2,3-epoxypropoxy)propyltrimethoxysilane: manufacturer: Aldrich Chemical Reagent Co., Ltd.;

[0092] Silicone modified epoxy resin: manufacturer: Youmei New Material Co., Ltd., brand: H26;

[0093] Polyurethane modified epoxy resin: manufacturer: Dow Chemical Company, brand: 791;

[0094] Phenolic modified epoxy resin: manufacturer: Dow Chemical Company, brand: 642;

[0095] TCPP: manufacturer: Macklin Biochemical Technology Co., Ltd.;

[0096] 0.03 mol% stannous octoate isopropyl alcohol solution: manufacturer: Aldrich Chemical Reagent Co., Ltd.

[0097] Example 1

[0098] Preparation of silicon-phosphorus flame retardant:

[0099] (1) 8 g of diethyl vinylphosphonate, 100 g of toluene and 0.08 g of 0.03 mol% isopropyl alcohol solution of chloroplatinic acid were sequentially added to a round-bottom flask, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80℃, and reacted for 1.5 h, then 4 g of dimethylsiloxy cage polysilsesquioxane was added to the above reaction system, and the reaction was continued for 4 h;

[0100] (2) The reaction product obtained in step (1) was filtered, and the solvent was removed, then the obtained product was placed in a vacuum oven at 80℃ and dried for 48 h, finally ground to obtain the silicon-phosphorus flame retardant.

[0101] By Figure 1 The infrared spectrum shown in the figure can be seen that the structure of the silicon-phosphorus flame retardant is shown as formula (4):

[0102]

[0103] Preparation of fireproof coating:

[0104] Component A: 45 g of bisphenol A type epoxy resin was added to a high-speed disperser, heated to 40℃, stirred at a speed of 1000 rpm for 1 h, then 15 g of pentaerythritol and 10 g of 3-aminopropyl triethoxysilane were added, stirred for 2 h, then 30 g of silicon-phosphorus flame retardant prepared in Example 1 was added, and stirred for 1 h, then discharged and packaged;

[0105] Component B: 15 g of diethylenetriamine was added to a high-speed disperser, heated to 40℃, stirred at a speed of 1000 rpm for 0.5 h, then 15 g of titanium dioxide, 15 g of melamine and 20 g of 3-aminopropyl triethoxysilane were added, and stirred for 2 h, then discharged and packaged.

[0106] Application of fireproof coating:

[0107] The component A and component B prepared in Example 1 were mixed in a mass ratio of 1:1, and then coated on the surface of a building by brushing to obtain a fireproof coating.

[0108] Example 2

[0109] Preparation of silicon-phosphorus flame retardant:

[0110] (1) 7 g of vinyl-1,1-tetraethyl diphosphate, 100 g of dimethylbenzene and 0.07 g of 0.03 mol% chloroplatinic acid isopropyl alcohol solution were sequentially added to a round-bottom flask, and the system was heated to 70°C under the action of nitrogen atmosphere and magnetic stirring, and reacted for 1.5 h. Then 3.5 g of dimethylsiloxy cage polysilsesquioxane was added to the above reaction system, and the reaction was continued for 4 h.

[0111] (2) The reaction product obtained in step (1) was filtered under suction to remove the solvent therein, and then the obtained product was placed in a 70°C vacuum oven for drying for 48 h, and finally ground to obtain a silicon-phosphorus flame retardant.

[0112] Preparation of fireproof coating:

[0113] Component A: 40 g of bisphenol F type epoxy resin was added to a high-speed disperser, heated to 40°C, and stirred at a speed of 1000 rpm for 1 h. Then 16 g of dipentaerythritol and 14 g of 3-aminopropyl trimethoxysilane were added, stirred for 2 h, and then 30 g of the silicon-phosphorus flame retardant prepared in Example 2 was added, and the stirring was continued for 1 h. The product was discharged and packaged.

[0114] Component B: 15 g of diethylenetriamine was added to a high-speed disperser, heated to 40°C, and stirred at a speed of 1000 rpm for 0.5 h. Then 15 g of titanium white powder, 15 g of melamine and 20 g of 3-aminopropyl triethoxysilane were added, and the stirring was continued for 2 h. The product was discharged and packaged.

[0115] Application of fireproof coating:

[0116] The component A and component B prepared in Example 2 were mixed in a mass ratio of 1:1, and then coated on the surface of a building by brushing to obtain a fireproof coating.

[0117] Example 3

[0118] Preparation of silicon-phosphorus flame retardant:

[0119] (1) 8 g dimethyl-vinylphosphonate, 100 g dichloro-sulfoxide and 0.08 g 0.03 mol% chloroplatinic acid in isopropanol were added into a round bottom flask in sequence, under nitrogen atmosphere and magnetic stirring, the system was heated to 60 °C, and reacted for 1.5 h. Then 4 g dimethylsiloxy cage polysilsesquioxane was added into the above reaction system, and reacted for another 4 h;

[0120] (2) The reaction product obtained in step (1) was filtered under suction, and the solvent was removed. Then the obtained product was dried in a vacuum oven at 60 °C for 36 h, and finally ground to obtain the silicon-phosphorus flame retardant.

[0121] Preparation of fireproof coating:

[0122] Component A: 40 g of acrylic modified epoxy resin was added into a high-speed disperser, heated to 40 °C, stirred at 1000 rpm for 1 h, then 20 g of linear starch and 15 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were added, stirred for 2 h, then 25 g of the silicon-phosphorus flame retardant prepared in Example 3 was added, and stirred for another 2 h. The product was discharged and packaged.

[0123] Component B: 10 g of triethylenetetramine was added into a high-speed disperser, heated to 40 °C, stirred at 1000 rpm for 0.5 h, then 12.5 g of aerogel powder, 12.5 g of melamine and 20 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were added, and stirred for another 2 h. The product was discharged and packaged.

[0124] Application of fireproof coating:

[0125] Component A and Component B prepared in Example 3 were mixed according to a mass ratio of 1:1, and then applied on the surface of equipment by brushing to obtain a fireproof coating.

[0126] Example 4

[0127] Preparation of silicon-phosphorus flame retardant:

[0128] (1) 9 g di-N-butylallylphosphonate, 100 g trichloromethane and 0.135 g 0.03 mol% chloroplatinic acid in isopropanol were added into a round bottom flask in sequence, under nitrogen atmosphere and magnetic stirring, the system was heated to 80 °C, and reacted for 1 h. Then 3.6 g dimethylsiloxy cage polysilsesquioxane was added into the above reaction system, and reacted for another 4 h.

[0129] (2) The reaction product obtained in step (1) was filtered under suction, and the solvent was removed. Then the obtained product was dried in a vacuum oven at 80 °C for 36 h, and finally ground to obtain the silicon-phosphorus flame retardant.

[0130] Preparation of fireproof coating:

[0131] Component A: 50 g of silicone-modified epoxy resin was added into a high-speed disperser, heated to 40 °C, stirred at 1000 rpm for 1 h, then 14 g of pentaerythritol and 11 g of 3-aminopropyl triethoxysilane were added, stirred for 2 h, then 25 g of the silicon-phosphorus flame retardant prepared in Example 4 was added, and stirred for another 1 h, and then discharged and packaged;

[0132] Component B: 20 g of triethylenetetramine was added into a high-speed disperser, heated to 40 °C, stirred at 1000 rpm for 0.5 h, then 15 g of titanium white, 10 g of melamine and 20 g of 3-aminopropyl triethoxysilane were added, and stirred for another 2 h, and then discharged and packaged.

[0133] Application of fireproof coating:

[0134] Component A and Component B prepared in Example 4 were mixed according to a mass ratio of 1:1, and then applied to the surface of the equipment by brushing to obtain a fireproof coating.

[0135] Example 5

[0136] Preparation of silicon-phosphorus flame retardant:

[0137] (1) 10 g of vinyl phosphonic acid diethyl ester, 100 g of N,N-dimethylformamide and 0.15 g of 0.03 mol% isopropanol solution of Castor were sequentially added into a round-bottom flask, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80 °C, and reacted for 2 h, then 4 g of dimethylsiloxy cage polysilsesquioxane was added into the above reaction system, and the reaction was continued for 3 h;

[0138] (2) The reaction product obtained in step (1) was filtered under suction to remove the solvent therein, and then the obtained product was placed in a vacuum oven at 80 °C for drying for 24 h, and finally ground to obtain the silicon-phosphorus flame retardant.

[0139] Preparation of fireproof coating:

[0140] Component A: 50 g of polyurethane-modified epoxy resin was added into a high-speed disperser, heated to 40 °C, stirred at 1000 rpm for 1 h, then 13 g of pentaerythritol and 17 g of 3-aminopropyl triethoxysilane were added, stirred for 2 h, then 20 g of the silicon-phosphorus flame retardant prepared in Example 5 was added, and stirred for another 1 h, and then discharged and packaged;

[0141] Component B: 18 g of tetraethylenepentamine was added into a high-speed disperser, heated to 40 °C, stirred at 1000 rpm for 0.5 h, then 15 g of fumed silica, 10 g of melamine and 15 g of 3-aminopropyl triethoxysilane were added, and stirred for another 2 h, and then discharged and packaged.

[0142] Application of the fireproof coating:

[0143] The component A and component B prepared in Example 5 were mixed in a mass ratio of 1:1, and then coated on the surface of a building by brushing to obtain a fireproof coating.

[0144] Example 6

[0145] Preparation of the silicon-phosphorus flame retardant:

[0146] (1) 6 g of vinyl-1,1-tetraethyl diphosphate, 100 g of toluene and 0.09 g of 0.03 mol% isopropanol solution of Castor were sequentially added into a round-bottom flask, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80°C, and reacted for 1 h, then 2.4 g of dimethylsiloxy cage polysilsesquioxane was added to the above reaction system, and the reaction was continued for 5 h;

[0147] (2) The reaction product obtained in step (1) was filtered under suction to remove the solvent therein, and then the obtained product was placed in a vacuum oven at 80°C for drying for 24 h, and finally ground to obtain the silicon-phosphorus flame retardant.

[0148] Preparation of the fireproof coating:

[0149] Component A: 50 g of phenolic modified epoxy resin was added into a high-speed disperser, heated to 40°C, stirred at a speed of 1000 rpm for 1 h, then 10 g of dipentaerythritol and 20 g of 3-aminopropyl trimethoxysilane were added, stirred for 2 h, then 20 g of the silicon-phosphorus flame retardant prepared in Example 6 was added, and the stirring was continued for 1 h, and then the product was discharged and packaged.

[0150] Component B: 15 g of tetraethylenepentamine was added into a high-speed disperser, heated to 40°C, stirred at a speed of 1000 rpm for 0.5 h, then 10 g of aerogel powder, 15 g of melamine and 20 g of 3-aminopropyl trimethoxysilane were added, and the stirring was continued for 2 h, and then the product was discharged and packaged.

[0151] Application of the fireproof coating:

[0152] The component A and component B prepared in Example 6 were mixed in a mass ratio of 1:1, and then coated on the surface of a building by brushing to obtain a fireproof coating.

[0153] Example 7

[0154] Preparation of the silicon-phosphorus flame retardant:

[0155] (1) 8 g dimethyl-vinylphosphonate, 100 g xylene and 0.04 g 0.03 mol% isopropanol solution of castor were added into a round bottom flask in turn, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80 °C, and reacted for 2 h. Then 6.4 g dimethylsiloxy cage polysilsesquioxane was added into the above reaction system, and the reaction was continued for 2 h;

[0156] (2) The reaction product obtained in step (1) was subjected to suction filtration to remove the solvent therein, and then the obtained product was placed in a vacuum oven at 80 °C for drying for 48 h. Finally, the silicon-phosphorus flame retardant was obtained by grinding.

[0157] Preparation of fireproof coating:

[0158] Component A: 30 g bisphenol A type epoxy resin was added into a high-speed disperser, heated to 40 °C, stirred at a speed of 1000 rpm for 1 h, then 5 g dipentaerythritol and 15 g 3-aminopropyltrimethoxysilane were added, stirred for 2 h, then 50 g silicon-phosphorus flame retardant prepared in Example 7 was added, and stirred for 1 h before discharging and packaging;

[0159] Component B: 10 g diethylenetriamine was added into a high-speed disperser, heated to 40 °C, stirred at a speed of 1000 rpm for 0.5 h, then 20 g titanium white, 20 g urea and 30 g 3-aminopropyltrimethoxysilane were added, and stirred for 2 h before discharging and packaging.

[0160] Application of fireproof coating:

[0161] Component A and Component B prepared in Example 7 were mixed according to a mass ratio of 1:1, and then applied on the surface of a building by brushing to obtain a fireproof coating.

[0162] Example 8

[0163] Preparation of silicon-phosphorus flame retardant:

[0164] (1) 8 g di-N-butylallylphosphonate, 100 g dichloro sulfoxide and 0.04 g 0.03 mol% isopropanol solution of chloroplatinic acid were added into a round bottom flask in turn, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80 °C, and reacted for 1.5 h. Then 5.33 g dimethylsiloxy cage polysilsesquioxane was added into the above solution, and the reaction was continued for 6 h;

[0165] (2) The reaction product obtained in step (1) was subjected to suction filtration to remove the solvent therein, and then the obtained product was placed in a vacuum oven at 80 °C for drying for 48 h. Finally, the silicon-phosphorus flame retardant was obtained by grinding.

[0166] Preparation of fireproof coating:

[0167] Component A: 30 g of bisphenol A type epoxy resin was added into a high speed disperser, heated to 40 °C, stirred at 1000 rpm for 1 h, then 5 g of amylopectin starch and 25 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were added, stirred for 2 h, then 40 g of the silicon-phosphorus flame retardant prepared in Example 8 was added, stirred for 1 h, and then discharged and packaged;

[0168] Component B: 10 g of diethylenetriamine was added into a high speed disperser, heated to 40 °C, stirred at 1000 rpm for 0.5 h, then 20 g of titanium white, 20 g of urea and 20 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were added, stirred for 2 h, and then discharged and packaged.

[0169] Application of the fireproof coating:

[0170] The component A and component B prepared in Example 8 were mixed according to a mass ratio of 1:1, and then applied on the surface of a building by brushing to obtain a fireproof coating.

[0171] Example 9

[0172] Preparation of the silicon-phosphorus flame retardant:

[0173] (1) 8 g of vinyl phosphonic acid diethyl ester, 100 g of toluene and 0.16 g of 0.03 mol% chloroplatinic acid isopropyl alcohol solution were sequentially added into a round bottom flask, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80 °C, and reacted for 1.5 h, then 2.91 g of dimethyl siloxy cage polysilsesquioxane was added into the above reaction system, and the reaction was continued for 4 h;

[0174] (2) The reaction product obtained in step (1) was filtered under suction to remove the solvent therein, and then the obtained product was placed in a vacuum oven at 80 °C for drying for 48 h, and finally ground to obtain the silicon-phosphorus flame retardant.

[0175] Preparation of the fireproof coating:

[0176] Component A: 60 g of bisphenol F type epoxy resin was added into a high speed disperser, heated to 40 °C, stirred at 1000 rpm for 1 h, then 25 g of amylopectin starch and 5 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were added, stirred for 2 h, then 10 g of the silicon-phosphorus flame retardant prepared in Example 9 was added, stirred for 1 h, and then discharged and packaged;

[0177] Component B: 20 g of triethylenetetramine was added into a high speed disperser, heated to 40 °C, stirred at 1000 rpm for 0.5 h, then 5 g of titanium white, 20 g of triazine and 10 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were added, stirred for 2 h, and then discharged and packaged.

[0178] Application of the fireproof coating:

[0179] The component A and component B prepared in Example 9 were mixed in a mass ratio of 1:1, and then coated on the surface of equipment by brushing to obtain a fireproof coating.

[0180] Example 10

[0181] Preparation of the silicon-phosphorus flame retardant:

[0182] (1) 8 g of diethyl vinylphosphonate, 100 g of toluene and 0.16 g of 0.03 mol% chloroplatinic acid isopropyl alcohol solution were sequentially added to a round-bottom flask, under the action of nitrogen atmosphere and magnetic stirring, the system was heated to 80°C, and reacted for 1.5 h, then 2.67 g of dimethyl siloxy cage polysilsesquioxane was added to the above reaction system, and the reaction was continued for 5 h;

[0183] (2) The reaction product obtained in step (1) was filtered under suction to remove the solvent, and then the obtained product was placed in a vacuum oven at 80°C and dried for 48 h, and finally ground to obtain a silicon-phosphorus flame retardant.

[0184] Preparation of the fireproof coating:

[0185] Component A: 60 g of bisphenol F type epoxy resin was added to a high-speed disperser, heated to 40°C, stirred at a speed of 1000 rpm for 1 h, then 15 g of pentaerythritol and 5 g of 3-aminopropyl triethoxysilane were added, stirred for 2 h, then 20 g of the silicon-phosphorus flame retardant prepared in Example 10 was added, and stirred for 1 h, then discharged and packaged;

[0186] Component B: 20 g of triethylenetetramine was added to a high-speed disperser, heated to 40°C, stirred at a speed of 1000 rpm for 0.5 h, then 20 g of titanium white powder, 5 g of triazine and 5 g of 3-aminopropyl triethoxysilane were added, and stirred for 2 h, then discharged and packaged.

[0187] Application of the fireproof coating:

[0188] The component A and component B prepared in Example 10 were mixed in a mass ratio of 1:1, and then coated on the surface of equipment by brushing to obtain a fireproof coating.

[0189] Comparative Example 1

[0190] It was implemented in the manner of Example 1, except that in the preparation of component A, the silicon-phosphorus flame retardant prepared in Example 1 was replaced by the same mass of flame retardant TCPP.

[0191] Comparative Example 2

[0192] In the same manner as in Example 1, except that 0.03 mol% of chloroplatinic acid in isopropanol solution was replaced by 0.03 mol% of stannous octoate in isopropanol solution when preparing the silicon-phosphorus flame retardant.

[0193] Test Example

[0194] Carbon layer compressive strength test: refer to test standard GB / T 7757;

[0195] Carbon layer thermal conductivity test: refer to test standard GB / T 10297;

[0196] Carbon layer fire resistance time test: refer to test standard GB 12441.

[0197] The fire-retardant coating coated on Examples 1-10 and Comparative Examples 1-2 was burned, and the carbon layer thickness, carbon layer compressive strength, carbon layer thermal conductivity and fire resistance time were detected. The results are shown in Table 1:

[0198] Table 1

[0199]

[0200]

[0201] As can be seen from the data of Examples 1-10 and Comparative Examples 1-2, the silicon-phosphorus flame retardant prepared by the method described in the present application can catalyze the polymer to dehydrate during the burning process, so that the carbon layer thickness reaches more than 33 mm, and the fire resistance time is prolonged to about 180 min.

[0202] Figure 1 The infrared spectrum of the silicon-phosphorus flame retardant prepared in Example 1 is shown in Figure 1. Figure 1 As can be seen from Figure 1, the silicon-hydrogen characteristic peak (Si-H 2150 cm -1 ) of the raw material (dimethylsiloxy cage polysilsesquioxane) of Example 1 completely disappeared in the product, indicating that the dimethylsiloxy cage polysilsesquioxane completely reacted. The phosphate ester characteristic peak (P=O 1250 cm -1 ) of the vinyl phosphoric acid diethyl ester appeared in the product, indicating that the product contained phosphate groups, and the target product was obtained.

[0203] Figure 2 The digital photos of the carbon layer of the fire-retardant coating prepared in Example 1 after burning are shown in Figures 2-4. Figure 2 As can be seen from Figures 2-4, the overall coating thickness of the fire-retardant coating is about 2 mm, and after the coating is burned, the carbon layer expands, and the coating thickness increases to about 40 mm after burning, indicating that the fire-retardant coating has good burning expansion effect.

[0204] Figure 3The carbon layer pressure strength-displacement graph of the fireproof coating prepared for example 1 and comparative example 2 is shown in Figure 1. Figure 3 It can be seen that the carbon layer of example 1 has better strength and can resist external force of 100 kPa, while the carbon layer of comparative example 2 has lower strength and can be collapsed by external force of about 10 kPa.

[0205] The above is only an embodiment of the present application, and does not limit the patent scope of the present application. Any equivalent transformation or direct or indirect application in other related technical fields based on the content of the present application is also included in the patent protection scope of the present application.

Claims

1. A silicon-phosphorus flame retardant, characterized in that: The silicon-phosphorus flame retardant contains a compound having a structure shown in formula (1), Wherein, R1 is hydrogen, C1-C3 alkyl or tetraethyl phosphate, and R2 is C1-C5 alkyl.

2. The silicon-phosphorus flame retardant according to claim 1, characterized in that R1 is hydrogen, methyl or tetraethyl phosphate, and R2 is methyl, ethyl or butyl.

3. A method for preparing a silicon-phosphorus flame retardant, characterized in that: The method comprises the following steps: (1) mixing an unsaturated phosphate, a solvent, a catalyst and a polysiloxane to react; (2) subjecting the reaction product obtained in step (1) to solid-liquid separation, and drying the solid phase; Wherein, the catalyst is chloroplatinic acid and / or Custer catalyst.

4. The method according to claim 3, characterized in that The unsaturated phosphate is a compound having a structure represented by formula (2) and / or a compound having a structure represented by formula (3), Wherein, R3 and R4 are each independently selected from methyl, ethyl, butyl and vinyl, R5 is vinyl, methoxy or propenyl; R6, R7, R8 and R9 are each independently selected from ethyl, methyl and propyl.

5. The method according to claim 3 or 4, characterized in that The unsaturated phosphate is selected from one or more of diethyl vinyl phosphate, tetraethyl vinyl-1,1-diphosphate, dimethyl vinyl phosphate and di-N-butyl allyl phosphonate.

6. The method according to any one of claims 3 to 5, characterized in that The polysiloxane is a cage-shaped polysilsesquioxane.

7. The method according to any one of claims 3 to 6, characterized in that The solvent is selected from one or more of toluene, xylene, chloroform, N,N-dimethylformamide and thionyl chloride.

8. The method according to any one of claims 3 to 7, characterized in that The weight ratio of the unsaturated phosphate to the polysiloxane is 1.25-3:3, preferably 2-2.5:1; Preferably, the weight ratio of the catalyst to the unsaturated phosphate is 0.5-2:100, more preferably 1-1.5:100; Preferably, the weight ratio of the total weight of the unsaturated phosphate and the polysiloxane to the solvent is 8-15:

100.

9. The method according to any one of claims 3 to 8, characterized in that In step (1), the reaction conditions include: temperature of 60-80° C. and time of 3-8 h.

10. A fire retardant coating, characterized in that: The fire retardant coating contains component A and component B, and the component A and the component B are stored separately, wherein the component A contains epoxy resin, polyol, a first silane coupling agent and a silicon-phosphorus flame retardant, and the component B contains a curing agent, an inorganic filler, an organic amine and a second silane coupling agent; the silicon-phosphorus flame retardant is the silicon-phosphorus flame retardant according to claim 1 or 2, or the silicon-phosphorus flame retardant prepared by the method according to any one of claims 3 to 9.

11. The fire retardant coating according to claim 10, characterized in that: Based on the total weight of component A as 100 weight percent, the content of the silicon-phosphorus flame retardant is 10-50 weight percent, the content of the polyol is 5-25 weight percent, the content of the epoxy resin is 30-60 weight percent, and the content of the first silane coupling agent is 5-25 weight percent.

12. The fire retardant coating according to claim 10 or 11, characterized in that: Based on the total weight of component B as 100 weight percent, the content of the curing agent is 10-40 weight percent, the content of the inorganic filler is 5-40 weight percent, the content of the organic amine is 10-40 weight percent, and the content of the second silane coupling agent is 10-40 weight percent.

13. The fire retardant coating according to claims 10-12, characterized in that: The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, acrylic modified epoxy resin, silicone modified epoxy resin, polyurethane modified epoxy resin and phenolic modified epoxy resin; Preferably, the polyol is selected from one or more of pentaerythritol, dipentaerythritol and amylose; Preferably, the curing agent is selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; Preferably, the inorganic filler is selected from one or more of titanium dioxide, fumed silica and aerogel powder; Preferably, the organic amine is selected from one or more of melamine, urea and triazine; Preferably, the first silane coupling agent and the second silane coupling agent are independently selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

14. The fire retardant coating according to claims 10-13, characterized in that: The component A is obtained by mixing the epoxy resin, the polyol, the first silane coupling agent and the silicon-phosphorus flame retardant at 30-50° C.; The component B is obtained by mixing the curing agent, the inorganic filler, the organic amine and the second silane coupling agent at 30-50°C.

15. Use of the fire retardant coating according to any one of claims 10 to 14, characterized in that: The application comprises: mixing component A and component B in the fire retardant coating, and then coating the obtained mixture on the surface of a building or equipment.

16. The use according to claim 15, characterized in that The weight ratio of the component A to the component B is 1-4:

1.

17. The use according to claim 15 or 16, characterized in that The coating method is spraying, brushing or steam coating.

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