CN115044208A - Preparation method of water-resistant double-metal hydroxide flame-retardant silicone rubber - Google Patents
Preparation method of water-resistant double-metal hydroxide flame-retardant silicone rubber Download PDFInfo
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Abstract
The invention designs a water-resistant type double-metal hydroxide flame-retardant silicone rubber, and researches the combustion performance and the water resistance of the silicone rubber; the layered metal hydroxide is modified on the halogen-free flame retardant, and the excellent gas-phase flame retardant capability and the catalytic char formation capability of the layered metal hydroxide are utilized to enhance the thermal stability; meanwhile, in order to improve the compatibility and the dispersibility of the flame retardant and rubber, silane is used for carrying out secondary hydrophobic modification on the flame retardant; the high-efficiency halogen-free intumescent flame retardant agent obtained by modification effectively improves the thermal stability and water resistance of the silicon rubber material; the implementation of the patent provides a new idea for the development of a halogen-free flame retardant system with high flame retardance, high cleanness and high efficiency, and simultaneously the lower addition amount also increases the economic benefit of the flame-retardant silicone rubber composite material.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a preparation method of water-resistant double-metal hydroxide flame-retardant silicone rubber.
Technical Field
Silicon Rubber (SR) is increasingly used as an external insulator in the fields of aerospace, biomedicine, electronics, electrical, etc., such as high voltage transmission lines, bushings, cable terminals, etc., due to its characteristics of light weight, high insulation, superior chemical resistance, etc. However, with the development of the electronic industry, the use environment of the SR is increasingly severe, especially in some specific environments, some properties of the SR, such as flammability, water resistance, mechanical properties, etc., severely limit its further application in the field of high performance requirements. Therefore, how to effectively improve the flame retardant property of the flame retardant without affecting other properties is one of the key problems to be solved;
generally, the addition of flame retardants is the most convenient way to meet the requirements. However, conventional flame retardants, including metal hydroxides and intumescent flame retardants, are inefficient and have poor compatibility, resulting in a dramatic decrease in SR processability and mechanical properties. Therefore, it is a great challenge to ensure the excellent other properties of SR while effectively improving the flame retardancy of SR. The SR flame-retardant system still has the key problems of low efficiency, poor compatibility, poor water resistance, large addition amount of a flame retardant and the like, so that the problem of further improving the application value of the SR composite material becomes a difficult problem;
the layered hydroxide is used as a novel environment-friendly nano flame retardant with a layered crystal structure, and receives more and more attention in a preparation system of a halogen-free flame retardant polymer. The layered metal hydroxides may not only release H 2 O and CO 2 The flame-retardant and smoke-inhibiting agent can dilute combustible gas, and can play a role of physical barrier for isolating flame and absorbing smoke particles, thereby effectively improving the flame-retardant and smoke-inhibiting performance of the matrix. However, when the layered metal hydroxide is added into a polymer, due to poor compatibility with the polymer and strong van der waals and electrostatic forces between layers, the layered metal hydroxide is easy to agglomerate in a matrix, and the flame retardant effect is not ideal;
the melamine polyphosphate is loaded with the layered metal hydroxide, and the excellent gas-phase flame retardant capability and the catalytic char formation capability of the layered metal hydroxide are utilized to enhance the thermal stability; meanwhile, in order to improve the compatibility and the dispersibility of the flame retardant and rubber, the polydimethylsiloxane is used for carrying out secondary hydrophobic modification on the flame retardant; the high-efficiency halogen-free intumescent flame retardant agent obtained by modification effectively improves the water resistance and the thermal stability of the silicon rubber material; the implementation of the patent provides a new idea for the development of a high-efficiency flame-retardant and multifunctional halogen-free flame retardant system, and also provides an experimental basis for researching the influence of the layered metal hydroxide on the intumescent flame retardant.
Disclosure of Invention
The invention specifically relates to a preparation method of water-resistant double-metal hydroxide flame-retardant silicone rubber; the modified layered metal hydroxide nanosheet loaded halogen-free flame retardant is prepared through hydrothermal reaction, and the successful preparation of the modified flame retardant is proved and the thermal property of the modified flame retardant is analyzed through infrared spectroscopy, EDS (electron-dispersive spectroscopy), static contact angle test and thermogravimetric test; preparing the modified flame retardant into a flame-retardant silicone rubber composite material with the addition of 5 percent; the limit oxygen index test and the UL-94 test visually prove the high-efficiency flame retardance of the composite material, and the water immersion test proves the improvement of the water resistance of the composite material.
The purpose of the invention is realized by the following technical scheme:
1. the preparation method of the water-resistant double-metal hydroxide flame-retardant silicone rubber is characterized by comprising the following steps:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of halogen-free flame retardant, placing the halogen-free flame retardant into a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension liquid A;
b. weighing 4.42g of divalent transition metal salt and 2.86g of trivalent transition metal salt, putting the divalent transition metal salt and the trivalent transition metal salt into a 100ml beaker, adding 50ml of deionized water, and stirring until the divalent transition metal salt and the trivalent transition metal salt are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of modifier and 0.5g of curing agent in 50ml of organic solvent, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with organic solvent for 3-5 times, and curing in a vacuum drying oven for 1 hr;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
preparation method of water-resistant bimetal hydroxide flame-retardant silicone rubber:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified intercalated metal hydroxide modified halogen-free flame retardant, then continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature;
c. taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts on the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine;
2. the preparation method of the water-resistant type double metal hydroxide flame-retardant silicone rubber according to claim 1, wherein the halogen-free flame retardant is one or a combination of melamine phosphate, melamine pyrophosphate and melamine polyphosphate;
3. the method for preparing water-resistant bimetal hydroxide flame-retardant silicone rubber according to claim 1, characterized in that the divalent transition metal salt is one of nickel nitrate, ferrous sulfate and copper nitrate;
4. the method for preparing a water-resistant type double metal hydroxide flame-retardant silicone rubber according to claim 1, wherein the trivalent transition metal salt is one of ferric nitrate, aluminum nitrate and cesium sulfate;
5. the method for preparing the water-resistant bimetal hydroxide flame-retardant silicone rubber according to claim 1, wherein the silicone rubber is one or a combination of vulcanized silicone rubber, dimethyl silicone rubber, methyl vinyl silicone rubber and fluorosilicone rubber;
6. the method for preparing water-resistant bimetal hydroxide flame-retardant silicone rubber according to claim 1, characterized in that the organic solvent is one or a combination of ethyl acetate, styrene, ethylene glycol and xylene;
7. the method for preparing the water-resistant double metal hydroxide flame-retardant silicone rubber according to claim 1, wherein the modifier is one or a combination of polydimethylsiloxane, simethicone, methyl methacrylate and silicone resin;
preferably, 3.8g of melamine polyphosphate is correspondingly dissolved in 100ml of deionized water in the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant, and in addition, 100ml of deionized water is correspondingly added into 4.42g of nickel nitrate and 2.86g of aluminum nitrate;
preferably, the organic solvent is ethyl acetate and the modifier is polydimethylsiloxane in the process of modifying the halogen-free flame retardant by the modified intercalated metal hydroxide. The proportion of the modifier to the flame retardant is 1: 10;
preferably, in the room-temperature vulcanized silicone rubber in the preparation method of the halogen-free intumescent flame retardant room-temperature vulcanized silicone rubber composite material, the addition ratio of the modified melamine polyphosphate to the vulcanized silicone rubber is 100: 5;
compared with the prior art, the invention has the beneficial effects that:
the melamine polyphosphate is modified by utilizing the capability of the layered metal hydroxide to catalyze into carbon, so that the flame retardant capability of the melamine polyphosphate is greatly improved, and the capability of catalyzing into carbon is enhanced; compared with the traditional chemical intumescent flame retardant, the halogen-free flame retardant prepared by the patent effectively solves the problems of single flame retardant mode at the temperature of 150 ℃ and 300 ℃ and low carbon residue rate after combustion at the temperature of more than 600 ℃; moreover, through secondary hydrophobic modification, the dispersity and the compatibility of the intercalated metal hydroxide nanosheet loaded halogen-free flame retardant in rubber are effectively improved, the addition amount of the flame retardant is reduced, and the flame retardant efficiency of the flame retardant is greatly improved; the water-resistant double-metal hydroxide flame-retardant silicone rubber has the advantages of clean and pollution-free raw materials, low cost price, no toxicity, no smoke, no halogen, low addition amount and the like, is harmless to the environment and human bodies, realizes effective conversion and utilization of natural resources, improves the added value of rubber materials, and can improve economic benefits due to the low addition amount, so the water-resistant double-metal hydroxide flame-retardant silicone rubber has good application potential.
Drawings
FIG. 1 is an infrared spectrum characterization of the flame retardant provided in example 1 before and after modification;
FIG. 2 is a representation of SEM spectra before and after modification of the flame retardant provided in example 1;
FIG. 3 is the static contact angle test results before and after modification of the flame retardant provided in example 1;
FIG. 4 is a TGA and DTG curve before and after modification of the flame retardant provided in example 1;
fig. 5 is a limit oxygen index test and UL-94 results of the flame retardant silicone rubber composite provided in example 1.
Detailed Description
The following examples are given for further details:
example 1:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of melamine polyphosphate, placing the melamine polyphosphate in a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension A;
b. weighing 4.42g of nickel nitrate and 2.86g of aluminum nitrate, putting the nickel nitrate and the aluminum nitrate into a 100ml beaker, adding 50ml of deionized water, and stirring until the nickel nitrate and the aluminum nitrate are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of polydimethylsiloxane and 0.5g of curing agent in 50ml of ethyl acetate, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with ethyl acetate for 3-5 times, and curing the wet powder in a vacuum drying oven for 1 h;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
-preparation of water-resistant intercalated metal hydroxide modified halogen-free flame-retardant silicone rubber composite material:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified halogen-free flame retardant modified by intercalated metal hydroxide, continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature; c. Taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts on the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine;
example 2:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of melamine pyrophosphate, placing the melamine pyrophosphate in a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension A;
b. weighing 4.42g of nickel nitrate and 2.86g of aluminum nitrate, putting the nickel nitrate and the aluminum nitrate into a 100ml beaker, adding 50ml of deionized water, and stirring until the nickel nitrate and the aluminum nitrate are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. putting the filter cake into a vacuum drying oven at 60 ℃ for drying for 12h, taking out, and grinding to obtain a product, namely the halogen-free flame retardant modified by the intercalated metal hydroxide;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of polydimethylsiloxane and 0.5g of curing agent in 50ml of ethyl acetate, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with ethyl acetate for 3-5 times, and curing the wet powder in a vacuum drying oven for 1 h;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
-preparation of water-resistant intercalated metal hydroxide modified halogen-free flame-retardant silicone rubber composite material:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified halogen-free flame retardant modified by intercalated metal hydroxide, continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature;
c. taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts on the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine;
example 3:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of melamine polyphosphate, placing the melamine polyphosphate in a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension liquid A;
b. weighing 4.42g of ferrous sulfate and 2.86g of cesium nitrate, placing the ferrous sulfate and the cesium nitrate into a 100ml beaker, adding 50ml of deionized water, and stirring until the ferrous sulfate and the cesium nitrate are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of polydimethylsiloxane and 0.5g of curing agent in 50ml of ethyl acetate, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with ethyl acetate for 3-5 times, and curing the wet powder in a vacuum drying oven for 1 h;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
-preparation of water-resistant intercalated metal hydroxide modified halogen-free flame-retardant silicone rubber composite:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified halogen-free flame retardant modified by intercalated metal hydroxide, continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature;
c. taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts on the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine;
example 4:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of melamine polyphosphate, placing the melamine polyphosphate in a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension liquid A;
b. weighing 4.42g of nickel nitrate and 2.86g of aluminum nitrate, putting the nickel nitrate and the aluminum nitrate into a 100ml beaker, adding 50ml of deionized water, and stirring until the nickel nitrate and the aluminum nitrate are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of organic silicon resin and 0.5g of curing agent in 50ml of ethyl acetate, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with ethyl acetate for 3-5 times, and curing the wet powder in a vacuum drying oven for 1 h;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
-preparation of water-resistant intercalated metal hydroxide modified halogen-free flame-retardant silicone rubber composite:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified halogen-free flame retardant modified by intercalated metal hydroxide, continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature;
c. taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts on the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine;
example 5:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of melamine polyphosphate, placing the melamine polyphosphate in a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension liquid A;
b. weighing 4.42g of nickel nitrate and 2.86g of aluminum nitrate, putting the nickel nitrate and the aluminum nitrate into a 100ml beaker, adding 50ml of deionized water, and stirring until the nickel nitrate and the aluminum nitrate are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of polydimethylsiloxane and 0.5g of curing agent in 50ml of dimethylbenzene, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with xylene for 3-5 times, and curing in a vacuum drying oven for 1 hr;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
-preparation of water-resistant intercalated metal hydroxide modified halogen-free flame-retardant silicone rubber composite material:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified halogen-free flame retardant modified by intercalated metal hydroxide, continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature;
c. taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts on the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine;
example 6:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of melamine polyphosphate, placing the melamine polyphosphate in a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension liquid A;
b. weighing 4.42g of nickel nitrate and 2.86g of aluminum nitrate, putting the nickel nitrate and the aluminum nitrate into a 100ml beaker, adding 50ml of deionized water, and stirring until the nickel nitrate and the aluminum nitrate are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of polydimethylsiloxane and 0.5g of curing agent in 50ml of ethyl acetate, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with ethyl acetate for 3-5 times, and curing the wet powder in a vacuum drying oven for 1 h;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
-preparation of water-resistant intercalated metal hydroxide modified halogen-free flame-retardant silicone rubber composite material:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 10g of modified halogen-free flame retardant loaded by intercalated metal hydroxide nanosheets, then continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature; c. And taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts at the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine.
Claims (7)
1. The preparation method of the water-resistant double-metal hydroxide flame-retardant silicone rubber is characterized by comprising the following steps:
the preparation process of the intercalated metal hydroxide modified halogen-free flame retardant comprises the following steps:
a. weighing 3.8g of halogen-free flame retardant, placing the halogen-free flame retardant into a 250ml three-necked bottle, adding 100ml of deionized water, heating to 40 ℃, and mechanically stirring for about 2 hours to obtain uniformly dispersed milky suspension liquid A;
b. weighing 4.42g of divalent transition metal salt and 2.86g of trivalent transition metal salt, putting the divalent transition metal salt and the trivalent transition metal salt into a 100ml beaker, adding 50ml of deionized water, and stirring until the divalent transition metal salt and the trivalent transition metal salt are completely dissolved to obtain a transparent solution B;
c. under the action of mechanical stirring, dropwise adding the solution B into the liquid A by using a constant flow pump, keeping the temperature at 40 ℃, adjusting the pH to 8-9 after the dropwise adding process is finished, and continuously stirring for 12 hours;
d. transferring the solution into a stainless steel sealed 200ml polytetrafluoroethylene reaction kettle, reacting in a 70 ℃ oven for 12h, and taking out;
d. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing for 3-5 times by using deionized water, and collecting a filter cake;
e. drying the filter cake in a vacuum drying oven at 60 ℃ for 12h, taking out, and grinding to obtain a product, namely the intercalation metal hydroxide modified halogen-free flame retardant;
-preparation of modified intercalated metal hydroxide modified halogen-free flame retardant:
a. dissolving 4.5g of modifier and 0.5g of curing agent in 50ml of organic solvent, then adding 2g of halogen-free flame retardant modified by intercalated metal hydroxide, keeping the temperature at 30 ℃, and stirring for 30 min;
b. vacuum filtering, repeatedly washing with organic solvent for 3-5 times, and curing in a vacuum drying oven for 1 hr;
d. taking out the filter cake, and grinding to obtain a product, namely the modified intercalated metal hydroxide modified halogen-free flame retardant;
preparation method of water-resistant bimetal hydroxide flame-retardant silicone rubber:
a. weighing 98g of room temperature vulcanized silicone rubber A component, placing the component in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 1000r/min, adding 5g of modified halogen-free flame retardant modified by intercalated metal hydroxide, continuing to stir for 1h, then increasing the mechanical stirring speed to 5000r/min, adding 1g of room temperature vulcanized silicone rubber B component, and continuing to stir for 15 min;
b. injecting the room temperature vulcanized silicone rubber mixed solution into a polytetrafluoroethylene mold, then putting the polytetrafluoroethylene mold into a vacuum drying oven for vacuumizing, and curing for 24 hours at room temperature;
c. and taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts at the edge, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the size suitable for the flame retardant test by using a cutting machine.
2. The method for preparing the water-resistant bimetal hydroxide flame-retardant silicone rubber according to claim 1, characterized in that the halogen-free flame retardant is one or a combination of melamine phosphate, melamine pyrophosphate and melamine polyphosphate.
3. The method for preparing water-resistant bimetal hydroxide flame-retardant silicone rubber according to claim 1, wherein the divalent transition metal salt is one of nickel nitrate, ferrous sulfate and copper nitrate.
4. The method for preparing a water-resistant type double metal hydroxide flame-retardant silicone rubber according to claim 1, wherein the trivalent transition metal salt is one of ferric nitrate, aluminum nitrate and cesium sulfate.
5. The method for preparing the water-resistant bimetal hydroxide flame-retardant silicone rubber according to claim 1, wherein the silicone rubber is one or a combination of vulcanized silicone rubber, dimethyl silicone rubber, methyl vinyl silicone rubber and fluorosilicone rubber.
6. The method for preparing a water-resistant type double metal hydroxide flame-retardant silicone rubber according to claim 1, wherein the organic solvent is one or a combination of ethyl acetate, styrene, ethylene glycol and xylene.
7. The method for preparing the water-resistant double metal hydroxide flame-retardant silicone rubber according to claim 1, wherein the modifier is one or a combination of polydimethylsiloxane, simethicone, methyl methacrylate and silicone resin.
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