CN113789056B - Preparation method of efficient physical-chemical synergistic flame-retardant silicone rubber composite material - Google Patents
Preparation method of efficient physical-chemical synergistic flame-retardant silicone rubber composite material Download PDFInfo
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Abstract
The invention designs a preparation method of an efficient physical-chemical synergistic flame-retardant silicone rubber composite material, and researches the combustion performance of the silicone rubber composite material; firstly, the halogen-free flame retardant is modified to prepare the modified halogen-free flame retardant, so that the modified halogen-free flame retardant has better thermal stability, compatibility and dispersibility in silicon rubber, and the char forming capability of the flame retardant is enhanced. And then the flame retardant is mixed with a physical intumescent flame retardant to prepare a synergistic flame retardant, so that a high-efficiency physical-chemical synergistic flame retardant system is constructed and applied to the preparation of the flame-retardant silicone rubber composite material. The synergistic flame retardant prepared by the method has the advantages of easy preparation of raw materials, low cost, no halogen, no toxicity, no smoke, green and high efficiency and the like, can realize effective utilization and conversion of natural resources, improves the additional value of materials, widens the application channel of the silicone rubber, and has better application potential.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a preparation method of an efficient physical-chemical synergistic flame-retardant silicone rubber composite material.
Background
As an important polymer material, the silicone rubber material refers to a rubber whose main chain is composed of silicon and oxygen atoms alternately, and the silicon atom is usually connected with two organic groups; due to the unique molecular structure, the silicon rubber has better heat resistance, electrical insulation, chemical stability and the like than other common rubbers; the advantages lead the silicon rubber material to be widely applied in the fields of electric power, war industry, chemical industry and the like; unfortunately, the silicone rubber material is flammable, has a Low Oxygen Index (LOI) value, and releases a large amount of smoke and particulate matter during combustion, thereby having great influence on the safety of life and property and environmental pollution; therefore, how to obtain the high-performance flame-retardant silicone rubber material becomes a key problem to be solved urgently in the material field;
aiming at the serious problems existing in the use of the traditional halogen-containing flame retardant, a halogen-free intumescent flame retardant system is generated and gradually becomes a research hotspot in the field of flame retardance in recent years; generally, halogen-free intumescent flame retardant systems are mainly divided into two types, namely physical intumescent flame retardants and chemical intumescent flame retardants;
expandable Graphite (EG), also known as Graphite Intercalation Compound (GIC), is a novel physically intumescent flame retardant that has been used in many flame retardant applications due to its non-toxicity, abundant raw materials, simple preparation process, low smoke yield, and the like advantages; expandable graphite is generally prepared by inserting atoms, molecules, and ions between flake graphite layers connected by weak van der waals force by using physical or chemical reaction, thereby enlarging the interlayer spacing of the flake graphite; after receiving enough heat, oxidation-reduction reaction occurs between the enlarged layers of the expandable graphite, and the expandable graphite instantaneously expands by hundreds of times along the z-axis direction of the crystal structure to form a worm-like structure with a plurality of ordered graphite sheets; these flakes can act as a protective layer for the polymer matrix to block heat and mass transfer during combustion; the incombustible gas released in the reaction enables the expandable graphite to work as an inert filler in a condensed phase and can also play a role in flame retardance by diluting the combustible gas and absorbing combustion heat in a gas phase; thus, the addition of expandable graphite to a polymeric material can delay the ignition time by limiting heat and mass transfer from the substrate to the heat source, thereby effectively choking the flame and preventing further decomposition; the chemical intumescent flame retardant mainly comprises a carbon source, an acid source and a gas source, wherein the acid source is heated and decomposed to generate acid with strong dehydration effect, the carbon source is esterified, then dehydrated and carbonized, and ammonia decomposed by the gas source expands a carbon layer to finally form a microporous carbon layer, so that air and heat conduction are isolated, and the purpose of flame retardance is achieved; most of the traditional methods for flame-retarding the silicon rubber material only add a single intumescent flame retardant, so that the defects of physical intumescent flame retardance and chemical intumescent flame retardance are not exposed; for example, expandable graphite alone may be excessively expanded by heat, resulting in a loose, insufficiently dense carbon layer; the flame retardant efficiency of the chemical intumescent flame retardant is too low when the chemical intumescent flame retardant is used alone; therefore, how to improve the efficiency of the halogen-free intumescent flame-retardant silicone rubber material becomes a bottleneck problem;
the patent aims at efficiently improving the flame retardant property of the silicon rubber material, and designs and prepares an efficient physical-chemical synergistic flame retardant silicon rubber composite material; in order to improve the flame retardant efficiency of the flame retardant, expandable graphite with a physical expansion flame retardant effect and melamine polyphosphate with a chemical expansion flame retardant are mixed according to a certain proportion, so that an efficient physical-chemical synergistic flame retardant system is constructed, the system is used for preparing a flame retardant silicone rubber composite material, and the synergistic char formation effect of the two flame retardant systems is further explored; the implementation of the patent provides a new idea for the development of a high-performance, clean and efficient halogen-free flame retardant system, and also provides an experimental basis for exploring a physical-chemical synergistic intumescent system.
Disclosure of Invention
The invention aims to particularly relate to a preparation method of an efficient physical-chemical synergistic flame-retardant silicone rubber composite material; the modified halogen-free flame retardant is prepared through hydrothermal reaction, and EDS (electron-discharge spectroscopy) energy spectrum proves the successful preparation of the modified halogen-free flame retardant; two flame retardants were mixed in a 1: 1, preparing a synergistic flame retardant, and preparing a flame-retardant silicone rubber composite material by adding 40 percent of the synergistic flame retardant; the high efficiency of the synergistic flame retardant was shown by limited oxygen index testing, UL-94 testing and thermogravimetric testing, as well as SEM testing and raman testing of the composite residue.
The purpose of the invention is realized by the following technical scheme:
1. the preparation method of the high-efficiency physical-chemical synergistic flame-retardant silicone rubber composite material is characterized by comprising the following steps:
-preparation of modified halogen-free flame retardant:
a. weighing 4.72g of halogen-free flame retardant and 3.27g of transition metal salt, putting into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for about 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. drying the filter cake in a vacuum drying oven at 70 ℃ for 12h, taking out, grinding into powder, weighing 5g of powder, placing in a 100ml beaker, adding 50ml of organic solvent, adding 0.5g of modifier, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with an organic solvent for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12 hours, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation process of flame retardant silicone rubber composite:
a. weighing 20g of halogen-free flame retardant and 20g of expandable graphite, placing the halogen-free flame retardant and the expandable graphite in an agate mortar, fully grinding for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. 98g of silicon rubber is weighed and placed in a 200mL polytetrafluoroethylene container, mechanical stirring is carried out at the speed of 500r/min, the mixed flame retardant is added, and then stirring is continued for 30 min. Then, the mechanical stirring speed is increased to 1000r/min, and after 2g of curing agent is added, continuous stirring is carried out for 5 min;
c. injecting the silicon 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;
d. 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 high-efficiency physical-chemical synergistic flame-retardant silicone rubber composite material 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 the efficient physically-chemically synergistic flame-retardant silicone rubber composite material according to claim 1, wherein the transition metal salt is one or a combination of transition metal salts such as nickel nitrate, zinc acetate and copper nitrate.
4. The method for preparing the efficient physico-chemical synergistic flame retardant silicone rubber composite material according to claim 1, characterized in that the organic solvent is one or a combination of toluene, ethyl acetate, tetrahydrofuran and xylene.
5. The method for preparing the high-efficiency physical-chemical synergistic flame-retardant silicone rubber composite material according to claim 1, wherein the modifier is one or a combination of epoxy modified silicone resin, methyl phenyl silicone resin and acrylic acid modified silicone resin.
6. The method for preparing the high-efficiency physical-chemical synergistic flame retardant silicone rubber composite material according to claim 1, wherein the expandable graphite has an expansion ratio of one or a combination of 50, 100, 200 and 500.
Compared with the prior art, the invention has the beneficial effects that:
the physical-chemical synergistic flame retardant is utilized, so that the flame retardant capability of the silicone rubber is enhanced efficiently, and the application range of the silicone rubber is widened; compared with the traditional single chemical intumescent flame retardant, the modified halogen-free flame retardant prepared by the patent effectively solves the problems of loose char formation and low flame retardant efficiency of the single flame retardant by loading transition metal; moreover, through hydrophobic modification, the dispersibility and compatibility of the halogen-free flame retardant in the silicone rubber are effectively improved, and the flame retardant efficiency of the flame retardant is greatly improved; and by adding the expandable graphite, the problems of low halogen-free flame-retardant char forming amount and the worm phenomenon of the expandable graphite are solved by virtue of the physical-chemical synergistic flame-retardant effect, and the compactness of the carbon layer is greatly improved. The preparation method of the efficient physical-chemical synergistic flame-retardant silicone rubber composite material has the advantages of being easy to prepare raw materials, low in cost, non-toxic, smokeless, halogen-free, efficient, environment-friendly and the like, realizes effective utilization and conversion of natural resources, and greatly improves the application value of the silicone rubber material. Therefore, the synergistic flame-retardant silicone rubber composite material obtained by the method has better application potential.
Drawings
FIG. 1 is an EDS spectrum characterization of the flame retardant provided in example 1 before and after modification.
FIG. 2 is the limiting oxygen index test and UL-94 results for the flame retardant silicone rubber composite provided in example 1.
Figure 3 is a TGA and DTG curve for different silicon sulfide samples provided in example 1.
FIG. 4 is a graph of the expansion effect at 600 ℃ for different samples of silicon sulfide provided in example 1.
Figure 5 is a scanned image of combustion residue before and after addition of expandable graphite as provided in example 1.
Fig. 6 is a raman test image of the flame retardant silicone rubber composite provided in example 1.
Detailed Description
The invention is further illustrated by the following examples; these examples are intended to illustrate the invention only and do not limit the scope of the invention; the raw materials, reagents and the like used in the following examples were obtained commercially from conventional markets and the like; the following examples are within the scope of the invention as claimed;
example 1:
-preparation of modified halogen-free flame retardant:
a. weighing 4.72g of melamine polyphosphate and 3.27g of nickel nitrate, placing the melamine polyphosphate and the nickel nitrate into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for about 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. drying the filter cake in a vacuum drying oven at 70 ℃ for 12h, taking out, grinding into powder, weighing 5g of powder, placing in a 100ml beaker, adding 50ml of ethyl acetate, adding 0.5g of epoxy modified organic silicon resin, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with ethyl acetate for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12h, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation of highly efficient physical-chemical synergetic flame-retardant silicone rubber composite:
a. weighing 20g of halogen-free flame retardant and 20g of expandable graphite with expansion multiplying power of 100 times, placing the mixture in an agate mortar with the diameter of 100 mm, fully grinding the mixture for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. 98g of silicon rubber is weighed and placed in a 200mL polytetrafluoroethylene container, mechanical stirring is carried out at the speed of 500r/min, the mixed flame retardant is added, and then stirring is continued for 30 min. Then, the mechanical stirring speed is increased to 1000r/min, and 2g of curing agent is added, and the stirring is continued for 5 min;
c. injecting the silicon 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;
d. 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.
Example 2:
-preparation process of modified halogen-free flame retardant:
a. weighing 4.72g of melamine pyrophosphate and 3.27g of nickel nitrate, placing the melamine pyrophosphate and the nickel nitrate into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for about 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. drying the filter cake in a vacuum drying oven at 70 ℃ for 12h, taking out, grinding into powder, weighing 5g of powder, placing in a 100ml beaker, adding 50ml of ethyl acetate, adding 0.5g of epoxy modified organic silicon resin, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with ethyl acetate for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12h, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation of highly efficient physical-chemical synergetic flame-retardant silicone rubber composite:
a. weighing 20g of halogen-free flame retardant and 20g of expandable graphite with expansion multiplying power of 100 times, placing the mixture in an agate mortar with the diameter of 100 mm, fully grinding the mixture for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. 98g of silicon rubber is weighed and placed in a 200mL polytetrafluoroethylene container, mechanical stirring is carried out at the speed of 500r/min, the mixed flame retardant is added, and then stirring is continued for 30 min. Then, the mechanical stirring speed is increased to 1000r/min, and after 2g of curing agent is added, continuous stirring is carried out for 5 min;
c. injecting the silicon 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;
d. 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.
Example 3:
-preparation of modified halogen-free flame retardant:
a. weighing 4.72g of melamine polyphosphate and 3.27g of copper nitrate, placing the melamine polyphosphate and the copper nitrate into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for about 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. drying the filter cake in a vacuum drying oven at 70 ℃ for 12h, taking out, grinding into powder, weighing 5g of powder, placing in a 100ml beaker, adding 50ml of ethyl acetate, adding 0.5g of epoxy modified organic silicon resin, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with ethyl acetate for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12h, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation of highly efficient physical-chemical synergetic flame-retardant silicone rubber composite:
a. weighing 20g of halogen-free flame retardant and 20g of expandable graphite with expansion multiplying power of 100 times, placing the mixture in an agate mortar with the diameter of 100 mm, fully grinding the mixture for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. 98g of silicon rubber is weighed and placed in a 200mL polytetrafluoroethylene container, mechanical stirring is carried out at the speed of 500r/min, the mixed flame retardant is added, and then stirring is continued for 30 min. Then, the mechanical stirring speed is increased to 1000r/min, and after 2g of curing agent is added, continuous stirring is carried out for 5 min;
c. injecting the silicon 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;
d. 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.
Example 4:
-preparation of modified halogen-free flame retardant:
a. weighing 4.72g of melamine polyphosphate and 3.27g of nickel nitrate, placing the melamine polyphosphate and the nickel nitrate into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for about 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. putting the filter cake into a vacuum drying oven at 70 ℃ for drying for 12h, taking out, grinding into powder, weighing 5g of powder, putting the powder into a 100ml beaker, adding 50ml of toluene, adding 0.5g of epoxy modified organic silicon resin, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with toluene for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12h, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation of highly efficient physical-chemical synergetic flame-retardant silicone rubber composite:
a. weighing 20g of halogen-free flame retardant and 20g of expandable graphite with expansion multiplying power of 100 times, placing the mixture in an agate mortar with the diameter of 100 mm, fully grinding the mixture for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. 98g of silicon rubber is weighed and placed in a 200mL polytetrafluoroethylene container, mechanical stirring is carried out at the speed of 500r/min, the mixed flame retardant is added, and then stirring is continued for 30 min. Then, the mechanical stirring speed is increased to 1000r/min, and after 2g of curing agent is added, continuous stirring is carried out for 5 min;
c. injecting the silicon 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;
d. 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.
Example 5:
-preparation process of modified halogen-free flame retardant:
a. weighing 4.72g of melamine polyphosphate and 3.27g of nickel nitrate, placing the melamine polyphosphate and the nickel nitrate into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for about 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. drying the filter cake in a vacuum drying oven at 70 ℃ for 12h, taking out, grinding into powder, weighing 5g of powder, placing in a 100ml beaker, adding 50ml of ethyl acetate, adding 0.5g of acrylic acid modified organic silicon resin, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with ethyl acetate for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12h, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation of highly efficient physical-chemical synergistic flame-retardant silicone rubber composite:
a. weighing 20g of halogen-free flame retardant and 20g of expandable graphite with expansion multiplying power of 100 times, placing the mixture in an agate mortar with the diameter of 100 mm, fully grinding the mixture for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. 98g of silicon rubber is weighed and placed in a 200mL polytetrafluoroethylene container, mechanical stirring is carried out at the speed of 500r/min, the mixed flame retardant is added, and then stirring is continued for 30 min. Then, the mechanical stirring speed is increased to 1000r/min, and after 2g of curing agent is added, continuous stirring is carried out for 5 min;
c. injecting the silicon 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;
d. 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 (3)
1. The preparation method of the efficient physical-chemical synergistic flame-retardant silicone rubber composite material is characterized by comprising the following steps:
-preparation of modified halogen-free flame retardant:
a. weighing 4.72g of halogen-free flame retardant and 3.27g of transition metal salt, putting into a 250ml three-necked bottle, adding 150ml of deionized water, heating to 40 ℃, and mechanically stirring for 4 hours to obtain uniformly dispersed suspension liquid;
b. 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;
c. drying the filter cake in a vacuum drying oven at 70 ℃ for 12h, taking out, grinding into powder, weighing 5g of powder, placing in a 100ml beaker, adding 50ml of organic solvent, adding 0.5g of modifier, keeping the temperature at 40 ℃, and stirring for 30 min;
d. pouring the mixed solution into a 100ml reaction kettle, sealing, and storing in a vacuum drying oven at 80 ℃ for 4 h;
e. when the temperature of the system is reduced to room temperature, carrying out vacuum filtration, repeatedly washing with an organic solvent for 3-5 times, collecting a filter cake, placing the filter cake in a vacuum drying oven at 70 ℃ for drying for 12 hours, taking out, and grinding to obtain a product, namely the modified halogen-free flame retardant;
-preparation process of flame retardant silicone rubber composite:
a. weighing 20g of modified halogen-free flame retardant and 20g of expandable graphite, placing the materials in an agate mortar, fully grinding the materials for 30min to obtain uniformly dispersed mixed flame retardant, and placing the mixed flame retardant in an oven at 60 ℃ for drying for 24 h;
b. weighing 98g of silicon rubber, placing the silicon rubber in a 200mL polytetrafluoroethylene container, mechanically stirring at the speed of 500r/min, adding the mixed flame retardant, and then continuing stirring for 30 min; then, the mechanical stirring speed is increased to 1000r/min, and after 2g of curing agent is added, continuous stirring is carried out for 5 min;
c. injecting the silicon 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;
d. taking the completely cured room temperature vulcanized silicone rubber composite material out of the mold, cutting off redundant parts at the edges, and cutting the room temperature vulcanized silicone rubber composite material sample plate into sample strips with the sizes suitable for flame retardant tests by using a cutting machine;
the halogen-free flame retardant is one or a combination of melamine phosphate, melamine pyrophosphate and melamine polyphosphate;
the transition metal salt is one or a combination of nickel nitrate, zinc acetate and copper nitrate;
the modifier is one or a combination of epoxy modified organic silicon resin, methyl phenyl silicon resin and acrylic acid modified organic silicon resin.
2. The method for preparing a high-efficiency physico-chemical synergistic flame retardant silicone rubber composite material according to claim 1, wherein the organic solvent is one or a combination of toluene, ethyl acetate, tetrahydrofuran and xylene.
3. The method for preparing the high-efficiency physically-chemically synergistic flame retardant silicone rubber composite material according to claim 1, wherein the expandable graphite is one or a combination of expandable graphite with expansion ratios of 50, 100, 200 and 500 times.
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| CN102516598A (en) * | 2011-12-08 | 2012-06-27 | 河北大学 | Melamine salt flame retardant and smoke suppressant agent and preparation method thereof |
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| WO2020173018A1 (en) * | 2019-02-28 | 2020-09-03 | 威海云山科技有限公司 | Modified expandable graphite and flame retardant, preparation method therefor, and use thereof in polyurethane foam |
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| CN102516598A (en) * | 2011-12-08 | 2012-06-27 | 河北大学 | Melamine salt flame retardant and smoke suppressant agent and preparation method thereof |
| CN105085983A (en) * | 2015-09-22 | 2015-11-25 | 清华大学深圳研究生院 | Halogen-free synergistic flame retardant, preparation method and composite flame retardant |
| WO2020173018A1 (en) * | 2019-02-28 | 2020-09-03 | 威海云山科技有限公司 | Modified expandable graphite and flame retardant, preparation method therefor, and use thereof in polyurethane foam |
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