Disclosure of Invention
The invention aims to solve the technical problem of providing a foam functional material for nuclear-grade equipment and a preparation method thereof aiming at the defects of the prior art. The invention provides a foam functional material for nuclear-grade equipment, which comprises raw materials of polyether polyol, polyester polyol, epoxy resin, a flame retardant, a foaming agent, a catalyst, a chloride ion fixing slurry and polyisocyanate, is 100 percent of domestic raw materials, has no soluble substances such as sulfur, fluorine, chlorine, bromine and the like, can be matched with metal equipment to jointly resist the working condition of serious accidents, and meets the service life requirement of 40 years.
In order to solve the technical problems, the invention adopts the technical scheme that: a foam functional material for nuclear-grade equipment is characterized by comprising the following components in parts by weight: 60-80 parts of polyether polyol, 10-20 parts of polyester polyol, 10-20 parts of epoxy resin, 40-50 parts of a flame retardant, 0.2-0.4 part of a foaming agent, 3.5-4 parts of a catalyst, 2-3 parts of a chloride ion fixing slurry and 170-200 parts of polyisocyanate; the polyether polyol is polyether I and polyether II; the flame retardant comprises diethyl ethylphosphonate, tri (dipropylene glycol) phosphite, melamine, ammonium polyphosphate, scandium sulfide and expanded vermiculite powder; the catalyst comprises dibutyltin dilaurate, potassium oleate, tetrabutyl titanate and tetrabutyl ammonium chloride; the polyisocyanate raw materials include polymeric MDI and 4, 4' -dicyclohexylmethane diisocyanate.
The foam functional material for the nuclear-grade equipment is characterized in that the polyether I has an average hydroxyl value of 480-500 mgKOH/g and viscosity of 6500mPa & s/25-9500 mPa & s/25 ℃; the average hydroxyl value of the polyether II is 280 mgKOH/g-340 mgKOH/g, and the viscosity is 900mPa & s/25-1700 mPa & s/25 ℃; the mass of the polyether II is 2 times of that of the polyether I.
The foam functional material for the nuclear-grade equipment is characterized in that the average hydroxyl value of the polyester polyol is 390 mgKOH/g-410 mgKOH/g, and the viscosity is 1.3Pa.s/25 ℃.
The foam functional material for the nuclear-grade equipment is characterized in that the epoxy resin is bisphenol A type epoxy resin, and the viscosity of the epoxy resin is less than 3000mPa & s/40 ℃.
The foam functional material for the nuclear-grade equipment is characterized in that the foaming agent is deionized water.
The foam functional material for the nuclear-grade equipment is characterized in that the chloride ion fixing slurry is slurry consisting of silver nitrate powder, an adhesive, a solvent and an auxiliary agent, silver nitrate is sieved by a 3000-mesh sieve, and the mass percentage of the silver nitrate in the chloride ion fixing slurry is 60-70%.
The foam functional material for the nuclear-grade equipment is characterized in that the mass of the polymeric MDI is 4 times that of 4, 4 '-dicyclohexylmethane diisocyanate, the average functionality of the polymeric MDI is 2.9-3.0, and the functionality of the 4, 4' -dicyclohexylmethane diisocyanate is 2.
In addition, the invention also provides a method for preparing the foam functional material for the nuclear-grade equipment, which is characterized by comprising the following steps:
step one, mixing polyether II, polyester polyol and diethyl ethylphosphonate under the stirring condition of 40-50 ℃ to obtain a material A;
secondly, sequentially adding melamine, ammonium polyphosphate, scandium sulfide, expanded vermiculite powder, dibutyltin dilaurate, potassium oleate, tetrabutyl titanate, a chloride ion fixing slurry and a foaming agent into the material A under the stirring condition of 40-50 ℃, and mixing to obtain a premix 1;
step three, stirring and mixing the polyether I and the epoxy resin uniformly under the stirring condition of 60-70 ℃ to obtain premix 2;
step four, stirring and mixing the polymeric MDI and the 4, 4' -dicyclohexylmethane diisocyanate under the stirring condition of 40-50 ℃ to obtain premix 3;
step five, sequentially adding the tris (dipropylene glycol) phosphite ester and tetrabutylammonium chloride into the premix 1 under the stirring condition of 40-50 ℃, and uniformly mixing to obtain a premix 4;
step six, mixing the premix 4, the premix 2 and the premix 3 to obtain a material B;
seventhly, introducing the material B into a mold under the water bath condition of 70-80 ℃, and sealing an exhaust port after the foam is full; the die is preheated in a water bath at the temperature of 70-80 ℃;
step eight, curing the mould filled with the foam in the step seven at the temperature of 140 ℃ for 12-18 h;
and step nine, cooling the die to be less than or equal to 50 ℃ after curing, taking out, and opening to obtain the foam functional material.
The method is characterized in that the stirring speed in the step one is 1000-1500 r/min; secondly, the stirring speed is 1500-2000 r/min; and thirdly, stirring at the speed of 5000-6000 r/min.
The method is characterized in that the stirring speed in the fourth step is 1000-1500 r/min; fifthly, the stirring speed is 1000-2000 r/min; and sixthly, the mixing speed is 2000-3000 r/min.
The parts can be measured in units of weight such as gram, two, jin, kilogram and ton.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a foam functional material for nuclear-grade equipment, which comprises raw materials of polyether polyol, polyester polyol, epoxy resin, a flame retardant, a foaming agent, a catalyst, a chloride ion fixing slurry and polyisocyanate, relates to 100% of domestic raw materials, has no soluble substances such as sulfur, fluorine, chlorine, bromine and the like, can be matched with metal equipment to resist nuclear accidents together, and meets the service life requirement of 40 years.
2. The invention provides a method for preparing the foam functional material for the nuclear-grade equipment, which comprises the steps of respectively obtaining a premix 1, a premix 2, a premix 3 and a premix 4, and mixing the premix 4, the premix 2 and the premix 3 to obtain a material B, wherein the material B is in a liquid phase in an initial form, can be easily injected into a cavity of the nuclear equipment to realize filling of the foam functional material, and the obtained foam functional material is a non-metal material with a low thermal conductivity coefficient and is easier to be matched with a metal nuclear equipment shell.
3. The invention has reliable principle and is beneficial to popularization and application.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Detailed Description
Example 1
The embodiment provides a foam functional material for nuclear-grade equipment, which comprises the following raw materials: 70 parts of polyether polyol, 20 parts of polyester polyol, 10 parts of epoxy resin, 49 parts of flame retardant, 0.2 part of foaming agent, 3.5 parts of catalyst, 2 parts of chloride ion fixing slurry and 180 parts of polyisocyanate; the polyether polyol is polyether I and polyether II; the flame retardant comprises 20 parts of diethyl ethylphosphonate, 10 parts of tris (dipropylene glycol) phosphite, 6 parts of melamine, 5 parts of ammonium polyphosphate, 5 parts of scandium sulfide and 3 parts of expanded vermiculite powder; the catalyst comprises 2.5 parts of dibutyltin dilaurate, 0.5 part of dibutyltin dilaurate, 0.3 part of potassium oleate, 0.1 part of tetrabutyl titanate and 0.1 part of tetrabutyl ammonium chloride; the polyisocyanate raw material comprises 144 parts of polymeric MDI and 36 parts of 4, 4' -dicyclohexylmethane diisocyanate;
wherein the average hydroxyl value of the polyether I is 480-500 mgKOH/g, and the viscosity is 6500 mPa.s/25-9500 mPa.s/25 ℃; the average hydroxyl value of the polyether II is 280 mgKOH/g-340 mgKOH/g, and the viscosity is 900 mPa.s/25-1700 mPa.s/25 ℃; the mass of the polyether II is 2 times of that of the polyether I; the polyether I is GR8349 produced from Shanghai high bridge petrochemical; the polyether II is GRW-310 produced from Shanghai high bridge petrochemical;
the polymerization degree of the ammonium polyphosphate is more than 1000, and the ammonium polyphosphate is produced by Shandong Shi An chemical engineering Co., Ltd; the expanded vermiculite powder is produced from Lingshou county Ruidaye, Inc.; the tri (dipropylene glycol) phosphite is produced by Cangzhou Wisco chemical;
the average hydroxyl value of the polyester polyol is 390mgKOH/g to 410mgKOH/g, and the viscosity is 1.3Pa.s/25 ℃; the polyester polyol is PS-4002 and is produced from Nanjing Jinling Spiral;
the epoxy resin is bisphenol A type epoxy resin, and the viscosity of the epoxy resin is less than 3000mPa.s/40 ℃; the epoxy resin is E51, produced by Shanghai resin factory;
the foaming agent is deionized water;
the chloride ion fixing slurry is slurry consisting of silver nitrate powder, an adhesive, a solvent and an auxiliary agent, wherein the silver nitrate is sieved by a 3000-mesh sieve, and the mass percentage of the silver nitrate in the chloride ion fixing slurry is 66%; the adhesive is epoxy resin, the solvent is isophorone, and the auxiliary agent is PEG-200;
the mass of the polymeric MDI is 4 times of that of 4, 4 '-dicyclohexylmethane diisocyanate, the average functionality of the polymeric MDI is 2.9-3.0, and the functionality of the 4, 4' -dicyclohexylmethane diisocyanate is 2; the polymeric MDI may be petunia PM-400, and the 4, 4' -dicyclohexylmethane diisocyanate (HMDI) may be HMDI produced from petunia;
in addition, the embodiment also provides a method for preparing the foam functional material for the nuclear-grade equipment, which comprises the following steps:
step one, mixing polyether II, polyester polyol and diethyl ethylphosphonate under the stirring condition of 40-45 ℃ to obtain a material A; the stirring speed of the mixing is 1500 r/min;
secondly, sequentially adding melamine, ammonium polyphosphate, scandium sulfide, expanded vermiculite powder, dibutyltin dilaurate, potassium oleate, tetrabutyl titanate, a chloride ion fixing slurry and a foaming agent into the material A under the stirring condition of 40-45 ℃, and mixing to obtain a premix 1; the stirring speed is 2000 r/min;
step three, stirring and mixing polyether I and epoxy resin under the stirring condition of 60-65 ℃ to obtain premix 2; the stirring speed is 5800 r/min;
step four, stirring and mixing the polymeric MDI and the 4, 4' -dicyclohexylmethane diisocyanate under the stirring condition of 40-45 ℃ to obtain premix 3; the stirring speed is 1500 r/min;
step five, sequentially adding the tris (dipropylene glycol) phosphite ester and tetrabutylammonium chloride into the premix 1 under the stirring condition of 40-45 ℃, and mixing to obtain a premix 4; the stirring speed is 1500 r/min;
step six, mixing the premix 4, the premix 2 and the premix 3 to obtain a material B; the stirring speed of the mixing is 3000 r/min;
seventhly, introducing the material B into a mold under the water bath condition of 70-75 ℃, carrying out chemical reaction on the material B until the material B is full of foam observed by naked eyes, and sealing an exhaust port; the die is preheated in a water bath at the temperature of 70-75 ℃;
step eight, curing the mould filled with the foam in the step seven at the temperature of 140 ℃ for 18 h;
and step nine, cooling the die to be less than or equal to 50 ℃ after curing, taking out, and opening to obtain the foam functional material.
Example 2
The embodiment provides a foam functional material for nuclear-grade equipment, which comprises the following raw materials: 80 parts of polyether polyol, 10 parts of polyester polyol, 10 parts of epoxy resin, 43 parts of flame retardant, 0.3 part of foaming agent, 4 parts of catalyst, 2.5 parts of chloride ion fixing slurry and 170 parts of polyisocyanate; the polyether polyol is polyether I and polyether II; the flame retardant comprises 19 parts of diethyl ethylphosphonate, 8 parts of tris (dipropylene glycol) phosphite, 9 parts of melamine, 3 parts of ammonium polyphosphate, 3 parts of scandium sulfide and 1 part of expanded vermiculite powder; the catalyst comprises 3.2 parts of dibutyltin dilaurate, 0.5 part of dibutyltin dilaurate, 0.1 part of potassium oleate, 0.1 part of tetrabutyl titanate and 0.1 part of tetrabutyl ammonium chloride; the polyisocyanate raw material comprises 136 parts of polymeric MDI and 34 parts of 4, 4' -dicyclohexylmethane diisocyanate;
wherein the average hydroxyl value of the polyether I is 480-500 mgKOH/g, and the viscosity is 6500 mPa.s/25-9500 mPa.s/25 ℃; the average hydroxyl value of the polyether II is 280 mgKOH/g-340 mgKOH/g, and the viscosity is 900 mPa.s/25-1700 mPa.s/25 ℃; the mass of the polyether II is 2 times of that of the polyether I; the polyether I is GR8349 produced from Shanghai high bridge petrochemical; the polyether II is GRW-310 produced from Shanghai high bridge petrochemical;
the polymerization degree of the ammonium polyphosphate is more than 1000, and the ammonium polyphosphate is produced by Shandong Shi An chemical engineering Co., Ltd; the expanded vermiculite powder is produced from Lingshou county Ruidaye, Inc.; the tris (dipropylene glycol) phosphite is produced by Cangzhou wafer chemical;
the average hydroxyl value of the polyester polyol is 390mgKOH/g to 410mgKOH/g, and the viscosity is 1.3Pa.s/25 ℃; the polyester polyol is PS-4002 and is produced from Nanjing Jinling Spiral;
the epoxy resin is bisphenol A type epoxy resin, and the viscosity of the epoxy resin is less than 3000mPa.s/40 ℃; the epoxy resin is E51, produced by Shanghai resin factory;
the foaming agent is deionized water;
the chloride ion fixing slurry is slurry consisting of silver nitrate powder, an adhesive, a solvent and an auxiliary agent, wherein the silver nitrate is sieved by a 3000-mesh sieve, and the mass percentage of the silver nitrate in the chloride ion fixing slurry is 68%; the adhesive is epoxy resin, the solvent is isophorone, and the auxiliary agent is PEG-200;
the mass of the polymeric MDI is 4 times of that of 4, 4 '-dicyclohexylmethane diisocyanate, the average functionality of the polymeric MDI is 2.9-3.0, and the functionality of the 4, 4' -dicyclohexylmethane diisocyanate is 2; the polymeric MDI may be petunia PM-400, and the 4, 4' -dicyclohexylmethane diisocyanate (HMDI) may be petunia HMDI;
in addition, the embodiment also provides a method for preparing the foam functional material for the nuclear-grade equipment, which comprises the following steps:
step one, mixing polyether II, polyester polyol and diethyl ethylphosphonate under the stirring condition of 45-50 ℃ to obtain a material A; the stirring speed of the mixing is 1000 r/min;
secondly, sequentially adding melamine, ammonium polyphosphate, scandium sulfide, expanded vermiculite powder, dibutyltin dilaurate, potassium oleate, tetrabutyl titanate, a chloride ion fixing slurry and a foaming agent into the material A under the stirring condition of 45-50 ℃, and mixing to obtain a premix 1; the stirring speed is 1500 r/min;
step three, stirring and mixing polyether I and epoxy resin under the stirring condition of 65-70 ℃ to obtain premix 2; the stirring speed is 5000 r/min;
step four, stirring and mixing the polymeric MDI and the 4, 4' -dicyclohexylmethane diisocyanate under the stirring condition of 45-50 ℃ to obtain premix 3; the stirring speed is 1000 r/min;
step five, sequentially adding the tris (dipropylene glycol) phosphite ester and tetrabutylammonium chloride into the premix 1 under the stirring condition of 45-50 ℃, and mixing to obtain a premix 4; the stirring speed is 1000 r/min;
step six, mixing the premix 4, the premix 2 and the premix 3 to obtain a material B; the stirring speed of the mixing is 2000 r/min;
seventhly, placing the material B in a mold under the water bath condition of 75-80 ℃, carrying out chemical reaction on the material B until the material B is full of foam observed by naked eyes, and sealing an exhaust port; the die is preheated in a water bath at the temperature of 75-80 ℃;
step eight, curing the mould filled with the foam in the step seven at 140 ℃ for 12 hours;
and step nine, cooling the die to be less than or equal to 50 ℃ after curing, taking out, and opening to obtain the foam functional material.
Example 3
The embodiment provides a foam functional material for nuclear-grade equipment, which comprises the following raw materials: 60 parts of polyether polyol, 20 parts of polyester polyol, 20 parts of epoxy resin, 46 parts of flame retardant, 0.4 part of foaming agent, 3.8 parts of catalyst, 3 parts of chloride ion fixing slurry and 191 parts of polyisocyanate; the polyether polyol is polyether I and polyether II; the flame retardant comprises 22 parts of diethyl ethylphosphonate, 9 parts of tris (dipropylene glycol) phosphite, 5 parts of melamine, 3 parts of ammonium polyphosphate, 5 parts of scandium sulfide and 2 parts of expanded vermiculite powder; the catalyst comprises 2.8 parts of dibutyltin dilaurate, 0.5 part of dibutyltin dilaurate, 0.1 part of potassium oleate, 0.1 part of tetrabutyl titanate and 0.3 part of tetrabutyl ammonium chloride; the polyisocyanate feed includes 152.8 parts of polymeric MDI and 38.2 parts of 4, 4' -dicyclohexylmethane diisocyanate;
wherein the average hydroxyl value of the polyether I is 480-500 mgKOH/g, and the viscosity is 6500 mPa.s/25-9500 mPa.s/25 ℃; the average hydroxyl value of the polyether II is 280 mgKOH/g-340 mgKOH/g, and the viscosity is 900 mPa.s/25-1700 mPa.s/25 ℃; the mass of the polyether II is 2 times of that of the polyether I; the polyether I is GR8349 produced from Shanghai high bridge petrochemical; the polyether II is GRW-310 produced from Shanghai high bridge petrochemical;
the polymerization degree of the ammonium polyphosphate is more than 1000, and the ammonium polyphosphate is produced by Shandong Shi An chemical engineering Co., Ltd; the expanded vermiculite powder is produced from Lingshou county Ruidaye, Inc.; the tris (dipropylene glycol) phosphite is produced by Cangzhou wafer chemical;
the average hydroxyl value of the polyester polyol is 390mgKOH/g to 410mgKOH/g, and the viscosity is 1.3Pa.s/25 ℃; the polyester polyol is PS-4002 and is produced from Nanjing Jinling Spiral;
the epoxy resin is bisphenol A type epoxy resin, and the viscosity of the epoxy resin is less than 3000mPa.s/40 ℃; the epoxy resin is E51, produced by Shanghai resin factory;
the foaming agent is deionized water;
the chloride ion fixing slurry is slurry consisting of silver nitrate powder, an adhesive, a solvent and an auxiliary agent, wherein the silver nitrate is sieved by a 3000-mesh sieve, and the mass percentage of the silver nitrate in the chloride ion fixing slurry is 61.8%; the adhesive is epoxy resin, the solvent is isophorone, and the auxiliary agent is PEG-200;
the mass of the polymeric MDI is 4 times of that of the 4, 4 '-dicyclohexylmethane diisocyanate, the average functionality of the polymeric MDI is 2.9-3.0, and the functionality of the 4, 4' -dicyclohexylmethane diisocyanate is 2; the polymeric MDI may be petunia PM-400, and the 4, 4' -dicyclohexylmethane diisocyanate (HMDI) may be petunia HMDI;
in addition, the embodiment also provides a method for preparing the foam functional material for the nuclear-grade equipment, which comprises the following steps:
step one, mixing polyether II, polyester polyol and diethyl ethylphosphonate under the stirring condition of 45-50 ℃ to obtain a material A; the stirring speed of the mixing is 1200 r/min;
secondly, sequentially adding melamine, ammonium polyphosphate, scandium sulfide, expanded vermiculite powder, dibutyltin dilaurate, potassium oleate, tetrabutyl titanate, a chloride ion fixing slurry and a foaming agent into the material A under the stirring condition of 45-50 ℃, and mixing to obtain a premix 1; the stirring speed is 1800 r/min;
step three, stirring and mixing polyether I and epoxy resin under the stirring condition of 65-70 ℃ to obtain premix 2; the stirring speed is 6000 r/min;
step four, stirring and mixing the polymeric MDI and the 4, 4' -dicyclohexylmethane diisocyanate under the stirring condition of 45-50 ℃ to obtain premix 3; the stirring speed is 1200 r/min;
step five, sequentially adding the tris (dipropylene glycol) phosphite ester and tetrabutylammonium chloride into the premix 1 under the stirring condition of 45-50 ℃, and mixing to obtain a premix 4; the stirring speed is 2000 r/min;
step six, mixing the premix 4, the premix 2 and the premix 3 to obtain a material B; the stirring speed of the mixing is 2500 r/min;
seventhly, placing the material B in a mold under the water bath condition of 75-80 ℃, carrying out chemical reaction on the material B until the material B is full of foam observed by naked eyes, and sealing an exhaust port; the die is preheated in a water bath at the temperature of 75-80 ℃;
step eight, curing the mould filled with the foam in the step seven at the temperature of 140 ℃ for 15 hours;
and step nine, cooling the die to be less than or equal to 50 ℃ after curing, taking out, and opening to obtain the foam functional material.
Performance evaluation:
the detection method and the detection result of the foam functional material for the nuclear-grade equipment in the examples 1-3 are shown in the tables 1 and 2.
TABLE 1 methods for Performance testing and standards in accordance therewith
TABLE 2 detection results of foam functional materials for nuclear-grade equipment
The carbon residue rate is judged to be qualified standard and is more than 10 percent.
The carbon residue determination may be performed by a scaled vessel, which may be the vessel shown in fig. 1; the container comprises a container body 1, wherein a cavity 2 for containing a foam functional material is formed in the container body, an air hole 3 is formed in the lower portion of the container body 1, a thermocouple 4 for measuring a test temperature is arranged at the lower portion of the container body 1, an electric heating source 5 for providing a heat source for the container body is arranged below the container body 1, and the container body is made of steel;
the mass of the container is recorded as m 1 The mass of the container after being filled with the foam functional material is m 2 Starting the thermal power supply to make the indication value of the thermocouple be a preset indication number, continuing for 40min, cooling, weighing the tested container, wherein the mass is m 3 (ii) a The carbon residue rate calculation formula is as follows:
the standard of qualification of the true fire test is as follows: the timing is started when the temperature of the outer surface of the device (the indication value of an external thermocouple) is more than 900 ℃, the timing lasts for 35min, the average temperature of the outer surface is more than 900 ℃, the device is wrapped by flame, and the temperature of the device is monitored in real time inside the device (the indication value of an internal thermocouple) is less than or equal to 150 ℃.
The true fire test method comprises the following steps: replacing the mold in the seventh embodiment with the device shown in fig. 2, wherein the device includes an annular cavity 6, the foam functional material is filled into the annular cavity 6 according to the embodiment, and the annular cavity 6 is provided with an exhaust hole 7; an internal thermocouple 8 for displaying the internal real-time temperature in the testing process and an external thermocouple 9 for displaying the external real-time temperature in the testing process are arranged on the equipment filled with the foam functional material; and (3) placing the equipment provided with the thermocouple in the oil pool 10, starting heating, enabling the indication value of the external thermocouple to be a preset indication value, continuing for 35min, and observing and recording the value of the internal thermocouple during the heating, namely the indication value of the internal thermocouple.
As can be seen from Table 2, the foam functional material prepared by the method of the present invention meets the requirements of nuclear-grade equipment.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.