CN112625643B - Organic silicon flame-retardant sealant and preparation method thereof - Google Patents
Organic silicon flame-retardant sealant and preparation method thereof Download PDFInfo
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- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses an organosilicon flame-retardant sealant and a preparation method thereof, belonging to the technical field of sealants. The product developed by the invention comprises the following raw materials in parts by weight: 80-100 parts of room temperature vulcanized methyl silicone rubber, 10-20 parts of dimethyl silicone oil, 3-5 parts of a silane coupling agent and 10-20 parts of a flame-retardant filler; the flame-retardant filler is phyllosilicate; the metal ions between the layers of the phyllosilicate are at least partially replaced by hydrogen ions; alginate is embedded between the layers of the layered silicate; the alginate is bound to the phyllosilicate skeleton via hydrogen bonds. In addition, the product also comprises spherical nano silicon dioxide with the mass of 5-10% of that of the room-temperature vulcanized methyl silicone rubber, and a heating reflux reaction device is used in the preparation step of the spherical nano silicon dioxide, so that the preparation method has the characteristics of high condensation rate and high reaction efficiency, and the prepared sealant has stable performance, higher physical and chemical strength and better flame retardant property.
Description
Technical Field
The invention relates to the technical field of sealants, in particular to an organic silicon flame-retardant sealant and a preparation method thereof.
Background
The organosilicon structural sealant is commonly called organosilicon structural adhesive in the building curtain wall decoration industry. The organic silicon structural adhesive is used as room temperature vulcanized (IHV) silicon rubber, does not need heating, illumination or other special conditions, can be vulcanized into an elastomer by contacting with moisture in the air at room temperature, and is very convenient to use. Meanwhile, due to the excellent high and low temperature resistance, good water resistance, excellent weather resistance, excellent and durable adhesion to various base materials (such as aluminum alloy, glass, metal, cement and the like), good elasticity and displacement resistance, the organic silicon structural adhesive is widely used in the building industry, especially the glass curtain wall decoration industry. As the building decoration industry has higher and higher requirements on the fire-proof level of buildings, the fire-proof performance of the glass curtain wall is concerned more and more; therefore, the flame retardancy of silicone structural adhesives is also receiving more and more attention.
The flame retardants such as aluminum hydroxide and decabromodiphenyl ether can endow the silicone rubber with flame retardant performance; but the amount is usually large, so other properties of the silicone rubber are affected. Particularly, after the flame retardant is added as an auxiliary agent, the migration is easy to occur in the actual use process of the product, and the actual flame retardant performance of the product is obviously reduced once a fire disaster occurs along with the prolonging of the service life, so that the effective flame retardant effect cannot be achieved.
Therefore, how to effectively improve the flame retardant performance of the product, avoid the migration of the flame retardant added in the product in the actual use process, and improve the flame retardant duration of the product is one of the directions developed by the technical personnel in the field.
However, in the preparation process of the flame-retardant sealant, because the traditional heating reflux reaction equipment has low cooling efficiency and low condensation rate, the reaction temperature of a controller cannot be accurately displayed and controlled, and the steam in the reaction process cannot be rapidly cooled, so that the reaction rate is influenced, and the production efficiency is reduced. Disclosure of Invention
The invention aims to provide an organosilicon flame-retardant sealant and a preparation method thereof, aiming at solving the defects that in the prior art, a flame retardant added in an organosilicon flame-retardant sealant is easy to migrate, so that the flame retardant performance of a product is continuously reduced along with the prolonging of the service life in the long-term service process, and the flame retardant is ineffective; meanwhile, the problem that in the step of preparing the spherical nano silicon dioxide, the used heating reflux reaction equipment has low cooling efficiency and low condensation rate, and the reaction temperature cannot be regulated and controlled at any time, so that the process production efficiency is influenced, and the yield of the sealant is limited is solved.
In order to achieve the purpose, the invention provides the following technical scheme:
an organosilicon flame-retardant sealant comprises the following raw materials in parts by weight:
80-100 parts of room-temperature vulcanized methyl silicone rubber
10-20 parts of dimethyl silicone oil
3-5 parts of silane coupling agent
10-20 parts of flame-retardant filler
The flame-retardant filler is phyllosilicate;
the metal ions between the layers of the phyllosilicate are at least partially replaced by hydrogen ions;
alginate is embedded between the layers of the layered silicate;
the alginate is bound to the phyllosilicate skeleton via hydrogen bonds.
The technical proposal utilizes the compound of the phyllosilicate and the alginate as the flame-retardant filler; firstly, because the molecular structure of the alginate contains more hydrophilic groups, and the layered silicate is also a polar inorganic filler, if the two are added separately, the compatibility with an organic resin matrix is poor, so that the phase separation of the flame-retardant components is caused, and the flame-retardant performance is reduced; according to the preparation method, the hydrophilic group in the alginate and the silicon hydroxyl group in the layered silicate are combined by compounding the hydrophilic group and the silicon hydroxyl group in the layered silicate, and a hydrogen bond is formed, so that polar groups on the surface are shielded mutually, and a nonpolar group of the alginate is exposed, so that the interface compatibility between the flame-retardant filler and a resin matrix is improved, and the flame-retardant filler can be well compatible with an organic resin matrix;
preferably, the organosilicon flame-retardant sealant also comprises spherical nano silicon dioxide accounting for 5-10% of the mass of the room-temperature vulcanized methyl silicone rubber.
Preferably, the spherical nano-silica is a hollow structure, and polystyrene acrylate is sealed in the hollow structure.
According to the technical scheme, the nano silicon dioxide with a hollow structure is further introduced into the system, the polystyrene acrylate is sealed and stored in the nano silicon dioxide, the polystyrene acrylate is decomposed under the high-temperature condition of fire, and the generated gas enables the nano silicon dioxide with the hollow structure to quickly float to the surface of the adhesive system, so that a hollow silicon dioxide protective layer is formed on the surface; due to the decomposition of polystyrene acrylate inside, the inside of the silicon dioxide hollow structure is in a nearly vacuum state, so that the heat conduction performance of the protective layer is remarkably reduced, heat cannot cause adverse effects on the inside of the adhesive, and the flame retardant property of the product is further improved;
preferably, the phyllosilicate is any one of sepiolite, montmorillonite, hectorite and hydrotalcite.
Preferably, the alginate is polyaldehyde alginate.
Preferably, the preparation method of the organosilicon flame-retardant sealant comprises the following steps:
the method comprises the following steps: pretreatment of the phyllosilicate: the method comprises the following steps of (1): 10-1: 20, mixing, pouring into a steam explosion tank, performing pressure maintaining treatment for 10-20min at the temperature of 200-220 ℃ and the pressure of 3.0-5.0MPa, then performing steam explosion treatment, collecting the explosion materials, washing, drying and calcining;
step two: pre-treating the composition of layered silicate and alginate, wherein the alginate and water are mixed according to the mass ratio of 1: 5-1: 10, standing for swelling after mixing, and heating, stirring and dissolving to obtain an alginate solution; mixing an alginate solution and a pretreated layered silicate according to a mass ratio of 5: 1-10: 1, mixing, carrying out ultrasonic impregnation, cooling, standing, carrying out suction filtration, washing and drying to obtain the flame-retardant filler;
according to the technical scheme, multi-aldehyde alginate is introduced into a product system, and sodium periodate is used for oxidizing alginate, so that hydroxyl in the molecular structure of alginate is oxidized into aldehyde, multi-aldehyde alginate is formed, under the high-temperature condition, the multi-aldehyde alginate can perform aldol condensation reaction with active hydroxyl in a layered silicate framework, water is generated, the generation of water can play a role in cooling, and after chemical bonding is performed between the alginate part and the layered silicate, the decomposition temperature of the alginate part and the layered silicate is higher, so that the flame-retardant and temperature-resistant performance of the product is further improved;
step three: the preparation of the product comprises the steps of sequentially taking 80-100 parts by weight of room-temperature vulcanized methyl silicone rubber, 10-20 parts by weight of dimethyl silicone oil, 3-5 parts by weight of silane coupling agent and 10-20 parts by weight of flame-retardant filler, uniformly mixing, discharging and packaging to obtain the organosilicon flame-retardant sealant.
Preferably, the organosilicon flame-retardant sealant also comprises spherical nano silicon dioxide accounting for 5-10% of the mass of the room-temperature vulcanized methyl silicone rubber; the spherical nano silicon dioxide is of a hollow structure, polystyrene acrylate is sealed and stored in the hollow structure, and the preparation method comprises the following steps:
according to the weight portion, 60-80 portions of glycerin, 8-10 portions of fatty acid, 8-10 portions of polystyrene acrylate and 8-10 portions of ethyl orthosilicate are taken in sequence, then one end of an air outlet pipe and one end of a liquid inlet pipe are respectively connected onto a reaction kettle, the other end of the air outlet pipe and one end of the liquid inlet pipe are connected into a condenser, a cooling liquid inlet of the condensation pipe are fixedly connected with a water outlet pipe, a cooling liquid outlet is fixedly connected with a water inlet pipe, the water outlet pipe and the water inlet pipe are connected with an external water tank, then 60-80 portions of glycerin, 8-10 portions of fatty acid, 8-10 portions of polystyrene acrylate and 8-10 portions of ethyl orthosilicate are added into the reaction kettle, a heating pipe is controlled by a controller to carry out heating and heat preservation, the temperature inside an outer casing is constantly monitored by a temperature sensor, steam generated by reaction inside the reaction kettle enters the condensation pipe along the air outlet pipe, and a compressor and the condenser outside the condensation pipe treat backflow condensate water, and (3) converting the steam in the snake-shaped condensing glass tube into liquid, refluxing the liquid along the liquid inlet tube into the reaction kettle, keeping the heating reflux reaction for 4 to 6 hours, filtering, washing and drying to obtain the spherical nano silicon dioxide.
Preferably, the alginate is polyaldehyde alginate, and the preparation process comprises the following steps:
mixing alginate and water according to a mass ratio of 1: 3-1: 10, mixing and pouring the mixture into a fermentation tank, adding bacillus subtilis accounting for 1-3% of the mass of alginate into the fermentation tank, then performing constant-temperature closed fermentation for 48-72 hours at the temperature of 30-35 ℃, starting the fermentation tank after the fermentation is finished, adding sodium periodate accounting for 5-10% of the mass of alginate, performing heating stirring reaction for 3-5 hours at the temperature of 75-85 ℃ and the rotation speed of 300-500r/min, and then filtering, washing and vacuum drying to obtain the polyaldehyde alginate.
Preferably, heating backward flow response device includes reation kettle, reation kettle includes outer covering and inner tube, inner tube one side fixed connection feed liquor pipe, a control valve of feed liquor pipe fixed connection, feed liquor pipe other end fixed connection condenser pipe, inner tube top fixed connection outlet duct, No. two control valves of fixed connection on the outlet duct, outlet duct other end fixed connection condenser pipe cools off the inside steam of reation kettle through the condenser pipe, and the process feed liquor pipe flows back to the inner tube and continues to refer to the reaction, No. two coolant liquid imports of condenser pipe and No. two coolant liquid exports are respectively through outlet pipe and inlet tube fixed connection on the water tank, water tank one side fixed connection compressor and condenser, compressor and condenser cool down the inside coolant liquid of condenser pipe.
The upper end fixedly connected with gear motor of reation kettle, the gear motor lower extreme is equipped with the (mixing) shaft, the other end fixed connection axle of (mixing) shaft, connecting rod No. one of connecting axle both ends fixed connection, fixed connection U type puddler on the connecting rod No. one, the inner wall of inner tube is hugged closely to U type puddler, avoids the reactant to glue the wall at the stirring in-process.
The heating pipe is wound on the outer wall of the inner barrel, the heating pipe is located between the outer casing and the inner barrel, the bottom of the heating pipe is fixedly connected with the controller, the upper end of the controller is fixedly connected with the temperature sensor, the temperature sensor is located between the casing and the inner barrel, the controller is provided with the display, the temperature of the cooling liquid of the controller is displayed by the display at any time, the controller is provided with the adjusting knob, and the adjusting knob controls the temperature of the heating pipe, so that the temperature required by the reaction of the inner barrel is changed.
Preferably, reation kettle bottom fixedly connected with support frame, the support frame includes supporting leg, stationary blade, gyro wheel and No. two connecting rods, the reation kettle bottom becomes triangular distribution fixed connection stationary blade, the fixed connection supporting leg on the stationary blade, the other end fixed connection gyro wheel of supporting leg, cross No. two connecting rod fixed connection between the supporting leg.
Preferably, the condenser pipe includes No. two coolant liquid exports, No. two coolant liquid imports, snakelike condensation glass pipe, No. two coolant liquid import fixed connection outlet pipes, No. two coolant liquid export fixed connection inlet tubes, the coolant liquid gets into by No. two coolant liquid imports of condenser pipe lower extreme, flows out by No. two coolant liquid exports again.
Preferably, a water inlet valve is fixedly connected to the first water inlet pipe, a water outlet valve is fixedly connected to the first water outlet pipe, a water supplementing pipe is fixedly connected to the upper end of the water tank, and a water supplementing valve is fixedly connected to the water supplementing pipe.
Preferably, the outer casing is provided with a first heat preservation liquid inlet, the outer casing is provided with a first heat preservation liquid outlet, the first heat preservation liquid inlet, and the outer casing is provided with a first heat preservation liquid outlet external device for preserving heat of reactants in the reaction kettle.
Advantageous effects
Compared with the prior art, the invention provides a preparation method of an organosilicon flame-retardant sealant, which has the following beneficial effects:
(1) the product obtained by the invention not only can obviously improve the cohesive strength of the product and obviously improve the strength of the product after curing, but also is not easy to phase separate and stable in property in the storage process due to the good compatibility between the flame-retardant filler and the resin matrix; and the loss is not easy to occur in the using process;
(2) the product obtained by the invention can quickly respond to the components with internal flame retardant property when abnormal high temperature occurs, and can react to further generate more stable substances besides forming a protective layer on the surface, so that the flame retardant property of the product is obviously improved.
(3) In the preparation step of the spherical nano silicon dioxide, the heating pipe is controlled by the controller of the heating reflux reaction equipment to heat and preserve heat, the temperature inside the outer casing is constantly detected by the temperature sensor and is displayed by the display, so that the reaction temperature can be accurately regulated and controlled; the inside reaction of reation kettle produces steam and gets into the condenser pipe along the outlet duct, and the outside compressor of condenser pipe and condenser are handled the comdenstion water of backward flow, turns into liquid along the feed liquor pipe in the reation kettle that flows back at the steam of snakelike condensation glass pipe, can effectual improvement condensing efficiency, is showing and has improved reaction efficiency.
Drawings
FIG. 1 is a block diagram of a process for preparing a silicone flame retardant sealant of the present invention;
FIG. 2 is a schematic view of a three-dimensional structure of a double-barrel reaction kettle with reflux condensation function according to the present invention;
FIG. 3 is a partial structure diagram of a double-barrel reaction kettle with reflux condensation function according to the present invention;
FIG. 4 is a structural diagram of a reaction kettle of a double-barrel reaction kettle with reflux condensation function according to the present invention;
FIG. 5 is a structural diagram of a stirring rod of a double-barrel reaction kettle with reflux condensation function according to the present invention;
FIG. 6 is a structural diagram of a support frame of a double-barrel reaction kettle with reflux condensation function according to the present invention;
FIG. 7 is a structural diagram of a heater of a double-barrel reaction kettle with reflux condensation function according to the present invention;
FIG. 8 is a structural diagram of a condenser tube of a double-barrel reaction kettle with reflux condensation function according to the present invention;
in the figure: 1. a reaction kettle; 101. an outer envelope; 102. an inner barrel; 103. a first heat preservation liquid inlet; 104. a first heat preservation liquid outlet; 105. a discharge port; 2. a reduction motor; 201. a stirring shaft; 202. a U-shaped stirring rod; 203. a connecting shaft; 204. a first connecting rod; 3. a support frame; 301. supporting legs; 302. a fixing sheet; 303. a roller; 304. a second connecting rod; 4. a condenser tube; 401. a second cooling liquid outlet; 402. a second cooling liquid inlet; 403. a serpentine condensing glass tube; 5. a water tank; 501. a condenser; 502. a compressor; 6. a water replenishing pipe; 601. a water replenishing valve; 7. a controller; 701. a temperature sensor; 702. heating a tube; 703. a display; 704. adjusting a knob; 8. a first water outlet pipe; 801. a first water outlet valve; 9. a first water inlet pipe; 901. a first water inlet valve; 10. a liquid inlet pipe; 1001. a first control valve; 11. an air outlet pipe; 1101. and a second control valve.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Referring to fig. 1-8, a method for preparing an organosilicon flame-retardant sealant.
Example 1
Preparing spherical nano silicon dioxide: taking 60 parts of glycerol, 8 parts of fatty acid, 8 parts of polystyrene acrylate and 8 parts of tetraethoxysilane in sequence according to parts by weight, mixing, pouring into a reaction kettle with a reflux condenser, heating, refluxing, reacting for 4 hours, filtering, washing and drying to prepare spherical nano silicon dioxide;
preparing multi-aldehyde alginate: mixing alginate and water according to a mass ratio of 1: 3, mixing and pouring the mixture into a fermentation tank, adding bacillus subtilis accounting for 1 percent of the mass of the alginate into the fermentation tank, then, carrying out constant-temperature closed fermentation for 48 hours at the temperature of 30 ℃, starting the fermentation tank after the fermentation is finished, adding sodium periodate accounting for 5 percent of the mass of the alginate, heating and stirring the mixture for reaction for 3 hours at the temperature of 75 ℃ and the rotating speed of 300r/min, and then, filtering, washing and vacuum drying the mixture;
pretreatment of the phyllosilicate: the method comprises the following steps of (1): 10, mixing, pouring into a steam explosion tank, performing pressure maintaining treatment for 10min at the temperature of 200 ℃ and the pressure of 3.0MPa, performing steam explosion treatment, collecting blasting materials, washing, drying and calcining to obtain pretreated layered silicate; the phyllosilicate is sepiolite;
pre-treating the composition of layered silicate and alginate: mixing polyaldehyde alginate and water according to a mass ratio of 1: 5, mixing, standing for swelling, and heating, stirring and dissolving to obtain an alginate solution; mixing an alginate solution and a pretreatment layered silicate according to a mass ratio of 5: 1, adding spherical nano silicon dioxide, carrying out ultrasonic impregnation for 3 hours at the ultrasonic frequency of 55kHz and the temperature of 55 ℃, cooling, standing to room temperature, carrying out suction filtration, washing and drying to obtain the flame-retardant filler;
preparation of the product: according to the weight parts, 80 parts of room temperature vulcanized methyl silicone rubber, 10 parts of dimethyl silicone oil, 3 parts of silane coupling agent and 10 parts of flame-retardant filler are sequentially taken, and are sheared and dispersed for 10min in a high-pressure homogenizer at the shearing rate of 1000r/min, and then the materials are discharged and packaged to prepare the organosilicon flame-retardant sealant.
Example 2
Preparing spherical nano silicon dioxide: taking 70 parts of glycerol, 9 parts of fatty acid, 9 parts of polystyrene acrylate and 9 parts of ethyl orthosilicate in sequence according to parts by weight, mixing and pouring the mixture into a reaction kettle with a reflux condenser, heating and refluxing for 5 hours, filtering, washing and drying to prepare spherical nano silicon dioxide;
preparing multi-aldehyde alginate: mixing alginate and water according to a mass ratio of 1: 5, mixing, pouring into a fermentation tank, adding bacillus subtilis accounting for 2% of the mass of alginate into the fermentation tank, then fermenting for 56 hours at a constant temperature in a closed manner at the temperature of 32 ℃, starting the fermentation tank after the fermentation is finished, adding sodium periodate accounting for 8% of the mass of alginate, heating, stirring and reacting for 4 hours at the temperature of 78 ℃ and the rotating speed of 400r/min, filtering, washing and drying in vacuum;
pretreatment of the phyllosilicate: the method comprises the following steps of (1): 15, mixing, pouring into a steam explosion tank, performing pressure maintaining treatment for 15min at the temperature of 210 ℃ and the pressure of 4.0MPa, performing steam explosion treatment, collecting explosion materials, washing, drying and calcining to obtain pretreated layered silicate; the phyllosilicate is montmorillonite;
pre-treating the composition of layered silicate and alginate: mixing polyaldehyde alginate and water according to a mass ratio of 1: 8, standing and swelling after mixing, and heating, stirring and dissolving to obtain an alginate solution; mixing an alginate solution and a pretreated layered silicate according to a mass ratio of 8: 1, adding spherical nano silicon dioxide, carrying out ultrasonic impregnation for 4 hours at the ultrasonic frequency of 60kHz and the temperature of 65 ℃, cooling, standing to room temperature, carrying out suction filtration, washing and drying to obtain the flame-retardant filler;
preparation of the product: according to the weight parts, 90 parts of room temperature vulcanized methyl silicone rubber, 15 parts of dimethyl silicone oil, 4 parts of silane coupling agent and 15 parts of flame-retardant filler are sequentially taken, and are sheared and dispersed for 15min in a high-pressure homogenizer at the shearing rate of 1500r/min, and then the materials are discharged and packaged to prepare the organosilicon flame-retardant sealant.
Example 3
Preparing spherical nano silicon dioxide: mixing 80 parts by weight of glycerol, 10 parts by weight of fatty acid, 10 parts by weight of polystyrene acrylate and 10 parts by weight of ethyl orthosilicate in sequence, pouring the mixture into a reaction kettle with a reflux condenser, heating and refluxing for 6 hours, filtering, washing and drying to prepare spherical nano silicon dioxide;
preparing multi-aldehyde alginate: mixing alginate and water according to a mass ratio of 1: 10, mixing, pouring into a fermentation tank, adding bacillus subtilis accounting for 3% of the mass of alginate into the fermentation tank, then fermenting at 35 ℃ for 72 hours in a constant-temperature closed manner, starting the fermentation tank after the fermentation is finished, adding sodium periodate accounting for 10% of the mass of alginate, heating and stirring for reacting for 5 hours at 85 ℃ and the rotating speed of 500r/min, filtering, washing and drying in vacuum;
pretreatment of the phyllosilicate: the method comprises the following steps of (1): 20, mixing, pouring into a steam explosion tank, performing pressure maintaining treatment for 20min at the temperature of 220 ℃ and the pressure of 5.0MPa, performing steam explosion treatment, collecting explosion materials, washing, drying and calcining to obtain pretreated layered silicate; the phyllosilicate is hectorite;
pre-treating the composition of layered silicate and alginate: mixing polyaldehyde alginate and water according to a mass ratio of 1: 10, standing for swelling after mixing, and heating, stirring and dissolving to obtain an alginate solution; mixing an alginate solution and a pretreatment layered silicate according to the mass ratio of 10: 1, adding spherical nano silicon dioxide, carrying out ultrasonic impregnation for 5 hours at the ultrasonic frequency of 65kHz and the temperature of 75 ℃, cooling, standing to room temperature, carrying out suction filtration, washing and drying to obtain the flame-retardant filler;
preparation of the product: according to parts by weight, 100 parts of room temperature vulcanized methyl silicone rubber, 20 parts of dimethyl silicone oil, 5 parts of silane coupling agent and 20 parts of flame-retardant filler are sequentially taken, and are cut and dispersed for 20min in a high-pressure homogenizer at the cutting rate of 2000r/min, and then the materials are discharged and packaged to prepare the organosilicon flame-retardant sealant.
Comparative example 1
The comparative example differs from example 1 in that: the alginate is directly used without introducing aldehyde group, and the other conditions are kept unchanged.
Comparative example 2
The comparative example differs from example 1 in that: polyaldehyde alginate is not added, and other conditions are kept unchanged.
Comparative example 3
This comparative example differs from example 1 in that: the hollow spherical nano silicon dioxide is not added, and the other conditions are kept unchanged.
Comparative example 4
Compared with example 1, the difference of the comparative example is that the common solid nano-silica and other mass substituted hollow spherical nano-silica are adopted, and the rest conditions are kept unchanged.
The products obtained in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, the specific test modes and test results are as follows:
and (3) testing mechanical properties: testing according to GB 16776-1997 organosilicon structural sealant for buildings; flame retardant property: testing is carried out according to a vertical method in GB/T2408 + 1996 plastic combustion performance test method, namely a horizontal method and a vertical method;
after the products obtained in examples 1-3 and comparative examples 1-4 were cured for 7d, the tensile bond strength and flame retardancy were tested; placing the mixture in an oven at the temperature of 80 ℃ for 200 hours, and testing the tensile bonding strength and the flame retardant property again, wherein the specific test results are shown in table 1;
table 1: product performance test results
The test results in table 1 show that the product obtained by the technical scheme of the application has stable performance, and the flame retardant property and the mechanical property of the sizing material can still be kept stable after long-term use.
Example 4
According to the technical scheme, the problems that the cohesive strength and the strength after curing of most organosilicon flame-retardant sealant products on the market are insufficient, the compatibility of the flame-retardant filler and a resin matrix is poor, the stability of the products is poor, the flame-retardant effect is poor and the like are solved, and in the process production work, the process production efficiency is influenced due to the fact that the condensation rate of the traditional heating reflux reaction equipment is low. As shown in fig. 2 to 8, in the heating reflux reaction apparatus used in the spherical nano-silica preparation step, the condensed water is cooled by the compressor and the condenser, so that the condensation rate is further increased, and the reaction temperature is constantly regulated and controlled by the temperature sensor, so that the heating reflux reaction efficiency is increased. The heating reflux reaction equipment comprises a reaction kettle 1, wherein the reaction kettle 1 comprises an outer casing 101 and an inner cylinder 102, one side of the inner cylinder 102 is fixedly connected with a liquid inlet pipe 10, the liquid inlet pipe 10 is fixedly connected with a control valve 1001, the other end of the liquid inlet pipe 10 is fixedly connected with a condenser pipe 4, the top end of the inner cylinder 102 is fixedly connected with a gas outlet pipe 11, the gas outlet pipe 11 is fixedly connected with a control valve 1101, the other end of the gas outlet pipe 11 is fixedly connected with the condenser pipe 4, steam in the reaction kettle 1 is cooled through the condenser pipe 4 and flows back to the inner cylinder 102 through the liquid inlet pipe 10 to continue to react, so that the reaction efficiency is improved, a second cooling liquid inlet 401 and a second cooling liquid outlet 402 of the condenser pipe 4 are respectively and fixedly connected to a water tank 5 through a water outlet pipe 8 and a water inlet pipe 9, one side of the water tank 5 is fixedly connected with a compressor 502 and a condenser 501, and the compressor 502 and the condenser 501 cool cooling liquid in the condenser 4, the condensed water is cooled by the compressor 502 and the condenser 501, so that the condensation rate is further improved. The reaction kettle comprises a reaction kettle 1, wherein the reaction kettle 1 comprises an outer shell 101 and an inner cylinder 102, one side of the inner cylinder 102 is fixedly connected with a liquid inlet pipe 10, the liquid inlet pipe 10 is fixedly connected with a first control valve 1001, the other end of the liquid inlet pipe 10 is fixedly connected with a condenser pipe 4, the top end of the inner cylinder 102 is fixedly connected with an air outlet pipe 11, the air outlet pipe 11 is fixedly connected with a second control valve 1101, the other end of the air outlet pipe 11 is fixedly connected with a condenser pipe 4, steam in the reaction kettle 1 is cooled through the condenser pipe 4 and flows back to the inner cylinder 102 through the liquid inlet pipe 10 to continue to react, so that the reaction efficiency is improved, a second cooling liquid inlet 401 and a second cooling liquid outlet 402 of the condenser pipe 4 are respectively and fixedly connected to a water tank 5 through a first water outlet pipe 8 and a first water inlet pipe 9, one side of the water tank 5 is fixedly connected with a compressor 502 and a condenser 501, the compressor 502 and the condenser 501 are used for cooling the cooling liquid in the condenser pipe 4, and the condensed water is cooled through the compressor 502 and the condenser 501, further increasing the condensation rate.
Further, in the above scheme, the heating pipe 702 is wound on the outer wall of the inner cylinder 102, the heating pipe 702 is located between the outer casing 101 and the inner cylinder 102, the controller 7 is fixedly connected to the bottom of the heating pipe 702, the temperature sensor 701 is fixedly connected to the upper end of the controller 7, the temperature sensor 701 is located between the outer casing 101 and the inner cylinder 102, the display 703 is arranged on the controller 7, the temperature of the cooling liquid of the controller 7 is constantly displayed on the display 703, the adjusting knob 704 is arranged on the controller 7, and the adjusting knob 704 controls the temperature of the heating pipe 702, so that the temperature required for the reaction of the inner cylinder 102 is changed, and the temperature required for the reaction in the reaction kettle 1 is constantly detected and controlled by arranging the heating pipe 702, the heating pipe 702 and the temperature sensor 701, and the reaction efficiency is improved.
Further, in above-mentioned scheme, 1 bottom fixedly connected with support frame 3 of reation kettle, support frame 3 includes supporting leg 301, stationary blade 302, gyro wheel 303 and No. two connecting rods 304, reation kettle 1 bottom becomes triangular distribution fixed connection stationary blade 302, fixed connection supporting leg 301 on the stationary blade 302, the other end fixed connection gyro wheel 303 of supporting leg 301, cross No. two connecting rods 304 fixed connection between the supporting leg 301, support frame 3 through the setting of reation kettle 1 bottom, the aspect of gyro wheel 303 that sets up the support frame 3 bottom shifts reation kettle 1.
Further, in above-mentioned scheme, condenser pipe 4 includes No. two coolant liquid export 401, No. two coolant liquid import 402, snakelike condensation glass pipe 403, No. two coolant liquid import 401 fixed connection outlet pipe 8, No. two coolant liquid export 402 fixed connection inlet tube 9, the coolant liquid gets into by No. two coolant liquid import 402 of condenser pipe 4 lower extreme, again by No. two coolant liquid export 401 outflow, reflux reation kettle 1 after being convenient for to the subsidiary reactant condensation of steam that the reaction produced through setting up condenser pipe 4.
Furthermore, in the above scheme, a first water inlet valve 901 is fixedly connected to a first water inlet pipe 9, a first water outlet valve 801 is fixedly connected to a first water outlet pipe 8, a water replenishing pipe 6 is fixedly connected to the upper end of the water tank 5, a water replenishing valve 601 is fixedly connected to the water replenishing pipe 6, and the first water inlet valve 901, the first water outlet valve 801 and the water replenishing valve 601 are arranged to facilitate the control of the liquid inlet and outlet.
Further, in the above scheme, be equipped with heat preservation liquid import 103 on outer shell 101, outer shell 101 is equipped with heat preservation liquid export 104, heat preservation liquid import 103, outer shell 101 is equipped with the external device of heat preservation liquid export 104 for keep warm to reation kettle 1 inside reactant, through heat preservation liquid import 103 and heat preservation liquid export 104, when needs cool down reation kettle 1, can effectively cool down, can cooperate heating pipe 702 when keeping warm to reation kettle 1, keep warm.
When using, through insert reation kettle 1 respectively with outlet duct 11 and feed liquor pipe 10 on, outlet duct 11 and feed liquor pipe 10 insert condenser pipe 4, No. two coolant liquid import 401 fixed connection outlet pipes 8 of condenser pipe 4, No. two coolant liquid export 402 fixed connection inlet tube 9, then with outlet pipe 8 and inlet tube 9 connection outside water tank 5. Adding the reactant into reaction kettle 1 again, then heating pipe 702 is controlled through controller 7 to heat and keep warm, temperature sensor 701 detects the inside temperature of outer envelope 101 constantly and shows through display 703, the inside reaction of reaction kettle 1 produces steam and gets into condenser pipe 4 along outlet duct 11, the outside compressor 502 of condenser pipe 4 and condenser 501 handle the comdenstion water of backward flow, effectual improvement condensing efficiency, turn into liquid along feed liquor pipe 10 backward flow in reaction kettle 1 at snakelike condensation glass pipe 403's steam, improve reaction efficiency.
When the condensing device is used, the air outlet pipe 11 and the liquid inlet pipe 10 are respectively connected onto the reaction kettle 1, the air outlet pipe 11 and the liquid inlet pipe 10 are connected into the condensing pipe 4, the second cooling liquid inlet 401 of the condensing pipe 4 is fixedly connected with the first water outlet pipe 8, the second cooling liquid outlet 402 is fixedly connected with the first water inlet pipe 9, the first water outlet pipe 8 and the first water inlet pipe 9 are connected with the external water tank 5, reactants are added into the reaction kettle 1, the heating pipe 702 is controlled by the controller 7 to heat for heat preservation, the temperature sensor 701 constantly detects the temperature inside the outer casing 101 and displays the temperature through the display 703, the steam generated by the reaction inside the reaction kettle 1 enters the condensing pipe 4 along the air outlet pipe 11, the compressor 502 and the condenser 501 outside the condensing pipe 4 treat the backflow condensed water, the condensing efficiency is effectively improved, the steam in the snake-shaped condensing glass pipe 403 is converted into liquid state and flows back into the reaction kettle 1 along the liquid inlet pipe 10, improve reaction efficiency, through support frame 3 that reation kettle 1 bottom set up, transfer reation kettle 1 in the aspect of the gyro wheel 303 that support frame 3 bottom set up.
When using, other end fixed connection condenser pipe through the feed liquor pipe, inner tube top fixed connection outlet duct, No. two control valves of fixed connection on the outlet duct, outlet duct other end fixed connection condenser pipe, through the condenser pipe to the inside steam cooling of reation kettle, continue to participate in the reaction in the inner tube through the feed liquor pipe reflux, thereby improve reaction efficiency, No. two coolant liquid import of condenser pipe and No. two coolant liquid exports respectively through an outlet pipe and a inlet tube fixed connection on the water tank, water tank one side fixed connection compressor and condenser, compressor and condenser are cooled down to condenser inside coolant liquid, cool down through the compressor and the condenser that set up to the water after the condensation, further improvement condensation rate.
When using, there is the heating pipe through the winding of inner tube outer wall, the heating pipe is located the centre of outer shell and inner tube, heating pipe bottom fixed connection controller, controller upper end fixed connection temperature sensor, the last centre that is located outer shell and inner tube of temperature sensor, be equipped with the display on the controller, the temperature of controller coolant liquid is shown often to the display, be equipped with adjust knob on the controller, adjust knob control heating pipe's temperature, thereby change the inner tube reaction and need the temperature, used setting up the heating pipe, heating pipe and temperature sensor detect and control reation kettle inside required temperature constantly, improve reaction efficiency.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference thereto is therefore intended to be embraced therein.
Claims (10)
1. The organic silicon flame-retardant sealant is characterized by comprising the following raw materials in parts by weight:
80-100 parts of room-temperature vulcanized methyl silicone rubber
10-20 parts of dimethyl silicone oil
3-5 parts of silane coupling agent
10-20 parts of flame-retardant filler
The flame-retardant filler is phyllosilicate;
the metal ions between the layers of the phyllosilicate are at least partially replaced by hydrogen ions;
alginate is embedded between the layers of the layered silicate;
the alginate is combined with the phyllosilicate framework through hydrogen bonds;
the organic silicon flame-retardant sealant also comprises spherical nano silicon dioxide accounting for 5-10% of the mass of the room-temperature vulcanized methyl silicone rubber;
the spherical nano silicon dioxide is of a hollow structure, and polystyrene acrylate is sealed and stored in the hollow structure;
the layered silicate is any one of sepiolite, montmorillonite, hectorite and hydrotalcite;
the alginate is polyaldehyde alginate.
2. The preparation method of the organic silicon flame-retardant sealant is characterized by comprising the following specific preparation steps:
the method comprises the following steps: pretreating the layered silicate, namely pretreating the layered silicate and hydrochloric acid according to a mass ratio of 1: 10-1: 20, mixing, pouring into a steam explosion tank, performing pressure maintaining treatment for 10-20min at the temperature of 200-220 ℃ and the pressure of 3.0-5.0MPa, then performing steam explosion treatment, collecting the explosion materials, washing, drying and calcining;
step two: pre-treating the composition of layered silicate and alginate, wherein the alginate and water are mixed according to the mass ratio of 1: 5-1: 10, adding spherical nano-silica after mixing, wherein the spherical nano-silica is of a hollow structure, and polystyrene acrylate is sealed and stored in the hollow structure; standing for swelling, and heating, stirring and dissolving to obtain alginate solution; mixing an alginate solution and a pretreated layered silicate according to a mass ratio of 5: 1-10: 1, mixing, carrying out ultrasonic impregnation, cooling, standing, carrying out suction filtration, washing and drying to obtain a flame-retardant filler;
step three: the preparation of the product comprises the steps of sequentially taking 80-100 parts by weight of room temperature vulcanized methyl silicone rubber, 10-20 parts by weight of dimethyl silicone oil, 3-5 parts by weight of silane coupling agent and 10-20 parts by weight of flame retardant filler, uniformly mixing, discharging and packaging to prepare the organosilicon flame retardant sealant.
3. The preparation method of the organosilicon flame-retardant sealant according to claim 2, wherein the spherical nano-silica accounts for 5-10% of the mass of the room temperature vulcanized methyl silicone rubber, and the preparation steps of the spherical nano-silica comprise:
according to the weight portion, 60-80 portions of glycerol, 8-10 portions of fatty acid, 8-10 portions of polystyrene acrylate and 8-10 portions of ethyl orthosilicate are mixed and placed in a reaction kettle of a heating reflux reaction device, and after the heating reflux reaction device is heated and refluxed for 4-6 hours, the mixture is filtered, washed and dried to prepare the spherical nano silicon dioxide.
4. The method for preparing the organosilicon flame-retardant sealant according to claim 2, wherein the alginate is polyaldehyde alginate, and the preparation process comprises:
mixing alginate and water according to a mass ratio of 1: 3-1: 10, mixing and placing in a fermentation tank, adding bacillus subtilis accounting for 1-3% of the mass of alginate into the fermentation tank, then fermenting at the constant temperature of 30-35 ℃ for 48-72h in a sealed manner, starting the fermentation tank after the fermentation is finished, adding sodium periodate accounting for 5-10% of the mass of alginate, heating and stirring for reacting for 3-5h at the temperature of 75-85 ℃ and the rotation speed of 300-500r/min, filtering, washing and drying in vacuum to obtain the polyaldehyde alginate.
5. The preparation method of the organosilicon flame retardant sealant according to claim 3, wherein the heating reflux reaction in the preparation step of the spherical nano-silica further comprises: respectively connecting one end of an air outlet pipe and one end of a liquid inlet pipe to a reaction kettle, connecting the other end of the air outlet pipe and one end of the liquid inlet pipe to a condenser, fixedly connecting a cooling liquid inlet of a condensation pipe to a water outlet pipe, fixedly connecting a cooling liquid outlet of the condensation pipe to a water inlet pipe, connecting the water outlet pipe and the water inlet pipe to an external water tank, adding reactants in parts by weight into the reaction kettle, controlling a heating pipe to heat and preserve heat by a controller, constantly monitoring the temperature inside an outer casing by a temperature sensor, enabling steam generated by reaction inside the reaction kettle to enter the condensation pipe along the air outlet pipe, processing reflowed condensate water by a compressor and the condenser outside the condensation pipe, and converting the steam in a snakelike condensation glass pipe into liquid state to reflow to the reaction kettle along the liquid inlet pipe;
the heating reflux reaction equipment comprises a reaction kettle (1), wherein the reaction kettle (1) comprises an outer casing (101) and an inner cylinder (102), one side of the inner cylinder (102) is fixedly connected with a liquid inlet pipe (10), the liquid inlet pipe (10) is fixedly connected with a first control valve (1001), the other end of the liquid inlet pipe (10) is fixedly connected with a condensing pipe (4), the top end of the inner cylinder (102) is fixedly connected with a gas outlet pipe (11), the gas outlet pipe (11) is fixedly connected with a second control valve (1101), the other end of the gas outlet pipe (11) is fixedly connected with the condensing pipe (4), steam in the reaction kettle (1) is cooled through the condensing pipe (4) and flows back to the inner cylinder (102) through the liquid inlet pipe (10) to continue to participate in reaction, a second cooling liquid outlet (401) and a second cooling liquid inlet (402) of the condensing pipe (4) are respectively and fixedly connected to a water tank (5) through a first water outlet pipe (8) and a first water inlet pipe (9), and one side of the water tank (5) is fixedly connected with a compressor (502) and a condenser (501), and the compressor (502) and the condenser (501) cool the cooling liquid in the condensation pipe (4).
6. The preparation method of the organosilicon flame retardant sealant according to claim 5, wherein a speed reduction motor (2) is fixedly connected to the upper end of the reaction kettle (1) in the heating reflux reaction equipment, a stirring shaft (201) is arranged at the lower end of the speed reduction motor (2), a connecting shaft (203) is fixed to the other end of the stirring shaft (201), a first connecting rod (204) is fixedly connected to both ends of the connecting shaft (203), a U-shaped stirring rod (202) is fixedly connected to the first connecting rod (204), the U-shaped stirring rod (202) is tightly attached to the inner wall of the inner cylinder (102), and reactants are prevented from being adhered to the wall in the stirring process.
7. The preparation method of the silicone flame retardant sealant according to claim 6, a heating pipe (702) is wound on the outer wall of the inner cylinder (102) in the heating reflux reaction equipment, the heating pipe (702) is positioned between the outer casing (101) and the inner barrel (102), the bottom of the heating pipe (702) is fixedly connected with a controller (7), the upper end of the controller (7) is fixedly connected with a temperature sensor (701), the temperature sensor (701) is positioned between the outer casing (101) and the inner cylinder (102), the controller (7) is provided with a display (703), the display (703) displays the temperature of the cooling liquid of the controller (7) at any time, the controller (7) is provided with an adjusting knob (704), and the adjusting knob (704) controls the temperature of the heating pipe (702), so that the temperature required by the reaction of the inner barrel (102) is changed.
8. The preparation method of the silicone flame retardant sealant according to claim 7, wherein a support frame (3) is fixedly connected to the bottom of the reaction kettle (1) in the heating reflux reaction equipment, the support frame (3) comprises support legs (301), fixing pieces (302), rollers (303) and a second connecting rod (304), the fixing pieces (302) are fixedly connected to the bottom of the reaction kettle (1) in a triangular distribution manner, the support legs (301) are fixedly connected to the fixing pieces (302), the rollers (303) are fixedly connected to the other ends of the support legs (301), and the support legs (301) are fixedly connected to the second connecting rod (304).
9. The method for preparing the silicone flame-retardant sealant according to claim 8, wherein the condensation tube (4) in the heating reflux reaction equipment comprises a second cooling liquid outlet (401), a second cooling liquid inlet (402) and a serpentine condensation glass tube (403), the second cooling liquid outlet (401) is fixedly connected with a first water outlet tube (8), the second cooling liquid inlet (402) is fixedly connected with a first water inlet tube (9), and cooling liquid enters from the second cooling liquid inlet (402) at the lower end of the condensation tube (4) and then flows out from the second cooling liquid outlet (401).
10. The preparation method of the silicone flame retardant sealant according to claim 9, wherein a first water inlet valve (901) is fixedly connected to the first water inlet pipe (9) in the heating reflux reaction equipment, a water outlet valve (801) is fixedly connected to the first water outlet pipe (8), a water replenishing pipe (6) is fixedly connected to the upper end of the water tank (5), and a water replenishing valve (601) is fixedly connected to the water replenishing pipe (6);
the reactor is characterized in that a first heat preservation liquid inlet (103) is formed in the outer casing (101), a first heat preservation liquid outlet (104) is formed in the outer casing (101), the first heat preservation liquid inlet (103), and a first heat preservation liquid outlet (104) external device is formed in the outer casing (101) and used for preserving heat of reactants in the reactor (1).
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