CN111003722A - Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive - Google Patents
Preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive Download PDFInfo
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- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive, which is used for preparing the activated calcium carbonate with the specific surface area of 20-25 m by a bubbling type carbonation reaction tower2The shape of the nano calcium carbonate is similar to that of a cube, a shape modifier is added for heating and aging, lime slurry is supplemented for low-speed carbonation, the calcium carbonate source can be increased, the recrystallization rate and the crystal growth rate of the calcium carbonate can be effectively accelerated, and finally sodium stearate is used for surface treatment and modification, so that the cube-like specific surface area with large particle size and regular shape is 7-12 m2The active calcium carbonate is effective in increasing the filling amount of the calcium carbonate in the colloid and ensuring that the two-component silicone adhesive has excellent flowingSex, thixotropy and mechanical property. The method also combines heating aging and low-speed carbonation to generate a synergistic effect, effectively shortens the aging time, improves the production efficiency, effectively recovers the carbonated tail gas, reduces the emission of carbon dioxide, and reduces the energy consumption and the production cost.
Description
Technical Field
The invention relates to the technical field of calcium carbonate preparation, in particular to a preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive.
Background
The organosilicon building sealant (commonly called as silicone adhesive, the same below) is an important component part of organosilicon high molecular materials, can be cured into elastic colloid by contacting with moisture in air at room temperature, is convenient to use, has the excellent characteristics of high and low temperature resistance, weather aging resistance, high electrical insulation and the like of common organosilicon materials, has the characteristics of good adhesion to various substrates, strong anti-displacement capability and the like, and has developed into an important sealing material for modern building decoration. The silicone adhesive can be divided into a single component (RTV-1) and a double component (RTV-2) according to the curing mode, wherein the RTV-1 is mainly used for small curtain walls and field construction, and the RTV-2 is mainly used for large curtain wall construction.
The silicone adhesive mainly comprises resin, filler and an auxiliary agent, wherein the resin and the filler account for more than 95% of the mass of the silicone adhesive, and the resin and the filler basically determine various performances of the silicone adhesive. The filler mainly plays a role in reinforcement and increment in the silicone adhesive, and can obviously improve the mechanical property of the silicone adhesive and reduce the cost of the silicone adhesive. At present, the filler of the silicone adhesive is mainly calcium carbonate and white carbon black, and under the double pressure of environmental protection and market competition, the calcium carbonate has gradually replaced the white carbon black to become the most main filler material of the silicone adhesive due to the reasons of huge raw material reserves, environmental production, low price, large filling amount, technical progress and the like of the calcium carbonate.
The calcium carbonate is mainly divided into heavy calcium carbonate, light calcium carbonate and nano calcium carbonate, wherein the heavy calcium carbonate has no reinforcing effect on the silicone adhesive and only plays a role in increasing and adjusting the fluidity of the adhesive, the light calcium carbonate is basically inapplicable to the silicone adhesive, the nano calcium carbonate can be widely applied to the silicone adhesive, the dispersibility in the adhesive is good, the reinforcing effect on the adhesive is strong, and the specific performance of the calcium carbonate in the silicone adhesive can be endowed through surface treatment modification. It was found by experiments that the effect of calcium carbonate on RTV-1 and RTV-2 is different, mainly due to the difference in the preparation process and the crosslinking agent. The invention mainly aims at RTV-2 silicone adhesive, can improve the filling amount of calcium carbonate to more than 65 percent, and ensures that the silicone adhesive has good thixotropy, fluidity and mechanical property.
In the silicone adhesive system, the particle size and morphology of calcium carbonate have a great influence on the performance of the filled silicone adhesive. The smaller the particle size of the calcium carbonate is, the better the mechanical property of the filling silicone adhesive is, and meanwhile, the poorer the fluidity of the filling silicone adhesive is, the smaller the filling amount of the calcium carbonate is and the higher the production cost is; the more regular the morphology of calcium carbonate, the better the flowability, thixotropy and mechanical properties of the filled silicone adhesive. Therefore, the preparation of the calcium carbonate with large particle size and regular morphology is an effective method for improving the filling amount of the calcium carbonate in the silicone adhesive and ensuring the fluidity, thixotropy and mechanical property of the filled silicone adhesive. At present, large-particle-size cubic calcium carbonate is difficult to directly prepare by adjusting a carbonization process, but spindle light calcium carbonate is directly prepared, the spindle light calcium carbonate is not suitable for being used in silicone adhesive, the prepared silicone adhesive has no contact change, and the flowability and the mechanical property are extremely poor. The large-particle-size cubic calcium carbonate can be prepared only by heating and aging a calcium carbonate suspension, during the aging process, Ostwald curing and particle surface rearrangement of the calcium carbonate occur, the calcium carbonate surface is re-modified, calcium carbonate crystals grow gradually, and finally the large-particle-size cubic calcium carbonate with regular appearance is obtained, but the problems of long aging time and high production cost exist at present.
Patent EP 0447094A 1 discloses a method for preparing rhombohedral calcium carbonate by accelerated thermal aging, which comprises the steps of heating a calcium carbonate suspension to 80 ℃, adding 2.0wt% of sodium hydroxide, keeping constant temperature and aging for 4-8 hours to obtain a product, or putting the calcium carbonate suspension into an autoclave, pressurizing to 500psi, heating to 200 ℃, keeping constant temperature and constant pressure and aging for 1-1.5 hours to obtain the product. The method is aged for 4-8 h at 80 ℃, the aging time is long, the production efficiency is low, and the production cost is high, or the aging time is shortened by aging for 1-1.5 h at 500psi and 200 ℃, but the aging equipment requirement is high, the energy consumption is high, and the production cost is high.
The patent refers to the field of 'processes or means for the direct conversion of chemical energy into electrical energy'. The method can obtain the cubic nano calcium carbonate with regular appearance, but has long aging time, low production efficiency and smaller product grain diameter, and can not meet the requirement of high filling.
The patent CN 104609453A discloses a preparation method of cubic precipitated calcium carbonate, wherein 0.5-3.0 wt% of urea and urease are added into a calcium carbonate suspension, the calcium carbonate suspension is heated to 60-90 ℃, kept at a constant temperature and aged for 2-15 h, and then subjected to surface treatment and modification to obtain the product. The method has the advantages of long aging time, low aging efficiency and small product particle size, and cannot meet the requirement of high filling.
The patent CN 107827137A discloses a preparation method of large-particle-size cubic precipitated calcium carbonate, which comprises the steps of carbonating calcium hydroxide slurry until the system conductivity is reduced to 0.5ms/cm, stopping introducing carbon dioxide, adding 0.3-1.0 wt% of a composite organic metal shielding agent, stirring for 20-40 min, keeping the temperature at 55-90 ℃ for aging for 1-4 h, introducing carbon dioxide again, carbonating to the end point, and finally carrying out surface treatment modification to obtain the product. Although the method can obtain products with large particle size, the accelerating aging agent selected by the method has the risk of flocculating calcium carbonate, is not beneficial to controlling the quality stability of the products, and has lower aging efficiency.
Generally speaking, heating and aging are effective methods for preparing large-particle-size cubic calcium carbonate, but the problems of low aging efficiency, high production energy consumption, unstable production and the like still exist at present, and the comprehensive requirements of industrial production and application markets are difficult to meet.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention provides a preparation method of activated calcium carbonate for high-filling-quantity bi-component silicone adhesive, aiming at the defects of the existing produced calcium carbonate filled silicone adhesive. The calcium carbonate prepared by the method has the advantages of good thixotropy, good fluidity, good mechanical property and the like, and can increase the filling amount of the calcium carbonate in silicone adhesive.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive comprises the following steps:
(1) calcining limestone at 1100-1300 ℃ for 300-500 min to obtain quicklime, carrying out digestion reaction on the quicklime and water to obtain lime slurry, sieving the lime slurry with a 100-mesh sieve to remove waste residues, and adjusting the solid content of the lime slurry to 10-13% for later use;
(2) feeding the lime slurry obtained in the step (1) into a carbonation reaction tower, starting a refrigeration cycle, adjusting the temperature of the lime slurry to 25-30 ℃, adding sucrose accounting for 0.01mt% of the mass of the lime slurry, introducing lime kiln recycle gas to start carbonation reaction, stopping introducing gas when the pH of a reaction system is 7.5, and stopping carbonation reaction to obtain a calcium carbonate suspension;
(3) and transferring the calcium carbonate suspension to a carbonation reaction tank containing a heat-preservation jacket, and adding a morphology modifier compounded by sodium salt and saccharides, wherein the addition amount of the morphology modifier is 0.5-2.0% of the dry mass of the calcium carbonate. Controlling the temperature of the suspension to be 55-70 ℃, starting low-speed stirring, introducing low-concentration carbon dioxide gas within 30-90 min, uniformly adding 5-10% of lime slurry based on the mass of the calcium carbonate suspension, and obtaining the calcium carbonate suspension with large particle size and similar cubic appearance;
(4) conveying the calcium carbonate suspension obtained in the step (3) to a treatment barrel, heating until the temperature of slurry is 55-70 ℃, adding a sodium stearate treatment agent accounting for 1.5-3.0% of the dry mass of calcium carbonate to perform surface treatment modification, and continuously stirring for 30-60 min to complete surface treatment;
(5) dehydrating, drying and crushing the calcium carbonate slurry subjected to surface treatment to obtain the calcium carbonate slurry with the specific surface area of 7-12 m2Per gram of activated calcium carbonate.
Further, the digestion reaction quicklime and water are mixed according to the mass ratio of the lime to the water of 1: 8-12, carrying out digestion reaction.
Further, the volume concentration of carbon dioxide in the lime kiln recycling gas in the step (2) is 30-35%, and the specific surface area of the calcium carbonate suspension is 20-25 m2Between/g.
Further, the sodium salt in the step (3) comprises one or more of sodium phosphate, sodium acetate and sodium oxalate.
Further, the saccharides of step (3) include glucose and/or sucrose.
Further, the mass ratio of the sodium salt to the saccharide is 3-1: 1.
Further, the low-concentration carbon dioxide gas in the step (3) is tail gas recovered from the carbonation reaction tower, and the volume concentration of the low-concentration carbon dioxide gas is 5-15%.
Further, the stirring rotation speed of the steps (2) and (4) is 3000r/min for 1000-.
Further, the drying is carried out for 24-48 h at the temperature of 110-125 ℃.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. according to the invention, nano calcium carbonate with the specific surface area of 20-25 m2/g is prepared through a bubbling type carbonation reaction tower, the shape is like a cube, a shape modifier is added for heating and aging, lime slurry is supplemented for low-speed carbonation, the speed of calcium carbonate source for effectively accelerating recrystallization and crystal growth of calcium carbonate can be increased, and finally sodium stearate is used for surface treatment and modification, so that the like cube with the large particle size and regular shape and the specific surface area of 7-12 m can be obtained2The active calcium carbonate/g can effectively improve the filling amount of the calcium carbonate in the colloid, and the bi-component silicone adhesive has excellent fluidity, thixotropy and mechanical property.
2. The method combines heating aging and low-speed carbonation to generate a synergistic effect, effectively shortens the aging time, improves the production efficiency, can effectively recover the carbonated tail gas, reduces the emission of carbon dioxide, slows down the greenhouse effect, fully utilizes the heat released by carbonation, and reduces the energy consumption and the production cost.
Drawings
FIG. 1 is a scanning electron microscope image of the active nano calcium carbonate of the embodiment 1 of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in further detail with reference to specific embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Example 1
A preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive comprises the following steps:
(1) crushing limestone to 2-3 cm of block size by using a jaw crusher, calcining at 1100 ℃ for 400min to obtain quicklime, carrying out digestion reaction on the quicklime and water according to the mass ratio of 1:11 of the greywater to obtain lime slurry, sieving the lime slurry by using a 100-mesh sieve to remove waste residues, adjusting the solid content of the lime slurry to 10.5%, aging the lime slurry and standing for 48 h;
(2) taking 15kg of lime slurry to feedStarting a carbonation reaction tower, starting a refrigeration cycle, adjusting the temperature of lime slurry to 29 ℃, adding 1.5g of cane sugar, starting stirring and refrigeration cycles, closing the refrigeration cycle after the temperature of the system reaches 29 ℃, adjusting the stirring speed to be 1500r/min, introducing mixed gas containing carbon dioxide to start reaction, controlling the flow rate of the carbon dioxide to be 2m 3/h, controlling the concentration of the carbon dioxide to be 33%, carbonating until the pH of the reaction mixture is 7.5, stopping introducing the gas, and stopping the carbonation reaction to obtain a calcium carbonate suspension liquid, wherein the specific surface area of the calcium carbonate suspension liquid is 21.08m2/g；
(3) Transferring the calcium carbonate suspension into a carbonation reaction tank with a heat-preservation jacket, adding a morphology modifier (sodium phosphate: glucose =2: 1) compounded by sodium salt and saccharides, wherein the addition amount of the morphology modifier is 1.0% of the dry mass of calcium carbonate, controlling the temperature of the suspension to be 60-65 ℃, starting the stirring speed to be 100r/min, continuously and uniformly adding lime slurry accounting for 5.0% of the mass of the calcium carbonate suspension into the calcium carbonate suspension in 30min, simultaneously introducing carbonation reaction tower tail gas, controlling the flow rate of carbon dioxide to be 0.5m 3/h, stopping introducing gas after 40min, and obtaining the calcium carbonate suspension with large particle size and similar cubic morphology;
(4) conveying the calcium carbonate suspension obtained in the step (3) to a treatment barrel, heating until the temperature of slurry is 60-65 ℃, adding a sodium stearate treatment agent with the mass of 2.0 percent of the dry basis mass of calcium carbonate for surface treatment modification, and continuously stirring for 45min at the rotating speed of 1500r/min to finish surface treatment;
(5) carrying out filter pressing and dehydration on the calcium carbonate slurry subjected to surface treatment, wherein the solid content of a filter cake is required to be more than or equal to 55%, transferring the filter cake into an oven to be dried for 24 hours at 115 ℃, and crushing and grading the dried filter cake to obtain the calcium carbonate slurry with the specific surface area of 8.78m2Per gram of activated calcium carbonate.
The active nano calcium carbonate product prepared by the embodiment is shown in figure 1 through a scanning electron microscope. The cubic calcium carbonate with regular appearance can be seen from the figure.
Example 2
A preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive comprises the following steps:
(1) crushing limestone to 2-3 cm of block size by using a jaw crusher, calcining at 1250 ℃ for 350min to obtain quicklime, adding 2kg of quicklime into tap water at 25 ℃ at one time according to the mass ratio of 1:11 of the quicklime, stirring for 20min, sieving lime slurry by using a 100-mesh sieve to remove waste residues, adjusting the solid content of the lime slurry to 11.5%, aging the lime slurry and standing for 48 h;
(2) feeding 15kg of lime slurry into a carbonation reaction tower, starting a refrigeration cycle, adjusting the temperature of the lime slurry to 26 ℃, adding 1.5g of cane sugar, starting stirring and refrigeration cycles, stopping the refrigeration cycle when the temperature of the system reaches 26 ℃, adjusting the stirring speed to 2000r/min, introducing mixed gas containing carbon dioxide to start reaction, and controlling the flow of the carbon dioxide to be 2m3H, the concentration of carbon dioxide is 33 percent, the gas is stopped to be introduced when the reaction mixture is carbonated until the pH value is 7.5, the carbonation reaction is stopped, and calcium carbonate suspension is obtained, wherein the specific surface area of the calcium carbonate suspension is 24.46m2/g；
(3) Transferring the calcium carbonate suspension to a carbonation reaction tank with a heat-preservation jacket, adding a morphology modifier (sodium acetate: glucose =3: 1) compounded by sodium salt and saccharides, wherein the addition amount of the morphology modifier is 1.5% of the dry mass of the calcium carbonate, controlling the temperature of the suspension to be 55-60 ℃, starting the stirring speed to be 120r/min, continuously and uniformly adding lime slurry accounting for 6.0% of the mass of the calcium carbonate suspension into the calcium carbonate suspension in 40min, simultaneously introducing the tail gas of a carbonation reaction tower, and controlling the flow rate of carbon dioxide to be 0.5m3The concentration of carbon dioxide in the tail gas of the carbonation reaction tower is 7-8%, and gas introduction is stopped after 50min to obtain a calcium carbonate suspension liquid with large particle size and similar cubic appearance;
(4) conveying the calcium carbonate suspension obtained in the step (3) to a treatment barrel, heating until the temperature of slurry is 55-60 ℃, adding a sodium stearate treatment agent with the mass of 2.5% of the dry basis mass of calcium carbonate for surface treatment modification, and continuously stirring for 30min at the rotating speed of 2000r/min to finish surface treatment;
(5) carrying out filter pressing dehydration on the calcium carbonate slurry subjected to surface treatment, transferring the filter cake with the solid content not less than 55% into an oven for drying at 120 ℃ for 26h, crushing and separating after dryingThe specific surface area of the obtained product is 10.63m2Per gram of activated calcium carbonate.
Example 3
A preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive comprises the following steps:
(1) crushing limestone to 2-3 cm of block size by using a jaw crusher, calcining at 1150 ℃ for 500min to obtain quicklime, adding 2kg of quicklime into 25 ℃ tap water at one time according to the mass ratio of 1:10 of the quicklime, stirring for 20min, sieving lime slurry by using a 100-mesh sieve to remove waste residues, adjusting the solid content of the lime slurry to 12.5%, aging the lime slurry and standing for 24 h;
(2) feeding 15kg of lime slurry into a carbonation reaction tower, starting a refrigeration cycle, adjusting the temperature of the lime slurry to 28 ℃, adding 1.5g of cane sugar, starting a stirring cycle and a refrigeration cycle, stopping the refrigeration cycle after the temperature of a system reaches 28 ℃, adjusting the stirring speed to be 1500r/min, introducing mixed gas containing carbon dioxide to start reaction, and controlling the flow of the carbon dioxide to be 2m3H, the concentration of carbon dioxide is 33 percent, the gas is stopped to be introduced when the reaction mixture is carbonated until the pH value is 7.5, the carbonation reaction is stopped, and calcium carbonate suspension is obtained, wherein the specific surface area of the calcium carbonate suspension is 22.35m2/g；
(3) Transferring the calcium carbonate suspension to a carbonation reaction tank with a heat-preservation jacket, adding a morphology modifier (sodium oxalate: glucose =3: 1) compounded by sodium salt and saccharides, wherein the addition amount of the morphology modifier is 1.8% of the dry mass of the calcium carbonate, controlling the temperature of the suspension to be 65-70 ℃, starting the stirring speed to be 150r/min, continuously and uniformly adding lime slurry accounting for 8% of the mass of the calcium carbonate suspension to the calcium carbonate suspension in 60min, simultaneously introducing the tail gas of a carbonation reaction tower, and controlling the flow rate of carbon dioxide to be 0.5m3The concentration of carbon dioxide in the tail gas of the carbonation reaction tower is 10-12%, and gas introduction is stopped after 30min to obtain a calcium carbonate suspension liquid with large particle size and similar cubic appearance;
(4) conveying the calcium carbonate suspension obtained in the step (3) to a treatment barrel, heating until the temperature of slurry is 65-70 ℃, adding a sodium stearate treatment agent with the mass of 3.0 percent of the dry basis mass of calcium carbonate for surface treatment modification, and continuously stirring for 45min at the rotating speed of 1500r/min to complete surface treatment;
(5) carrying out filter pressing and dehydration on the calcium carbonate slurry subjected to surface treatment, wherein the solid content of a filter cake is required to be more than or equal to 55%, transferring the filter cake into an oven for drying for 48h at 110 ℃, and crushing and grading after drying to obtain the calcium carbonate slurry with the specific surface area of 11.55m2Per gram of activated calcium carbonate.
Example 4
A preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive comprises the following steps:
(1) crushing limestone to 2-3 cm of block size by using a jaw crusher, calcining at 1300 ℃ for 400min to obtain quicklime, adding 2kg of quicklime into tap water at 30 ℃ at a ratio of 1:11 by mass of the gray water, stirring for 30min, sieving lime slurry by using a 100-mesh sieve to remove waste residues, adjusting the solid content of the lime slurry to 11.8%, aging the lime slurry and standing for 36%;
(2) feeding 15kg of lime slurry into a carbonation reaction tower, starting a refrigeration cycle, adjusting the temperature of the lime slurry to 25 ℃, adding 1.5g of cane sugar, starting stirring and refrigeration cycles, stopping the refrigeration cycle when the temperature of the system reaches 25 ℃, adjusting the stirring speed to 2000r/min, introducing mixed gas containing carbon dioxide to start reaction, and controlling the flow of the carbon dioxide to be 2m3H, the concentration of carbon dioxide is 33 percent, the gas is stopped to be introduced when the reaction mixture is carbonated until the pH value is 7.5, the carbonation reaction is stopped, and calcium carbonate suspension is obtained, wherein the specific surface area of the calcium carbonate suspension is 21.64m2/g；
(3) Transferring the calcium carbonate suspension to a carbonation reaction tank with a heat-preservation jacket, adding a morphology modifier (sodium oxalate: sucrose =2: 1) compounded by sodium salt and saccharides, wherein the addition amount of the morphology modifier is 1.5% of the dry mass of the calcium carbonate, controlling the temperature of the suspension to be 65-70 ℃, starting the stirring speed to be 100r/min, continuously and uniformly adding 7% of lime slurry of the mass of the calcium carbonate suspension to the calcium carbonate suspension within 40min, simultaneously introducing the tail gas of a carbonation reaction tower, and controlling the flow rate of carbon dioxide to be 0.5m3The concentration of carbon dioxide in the tail gas of the carbonation reaction tower is 7-8%, and gas introduction is stopped after 30min to obtain a calcium carbonate suspension liquid with large particle size and similar cubic appearance;
(4) conveying the calcium carbonate suspension obtained in the step (3) to a treatment barrel, heating until the temperature of slurry is 65-70 ℃, adding a sodium stearate treatment agent with the mass of 2.5 percent of the dry basis mass of calcium carbonate for surface treatment modification, and continuously stirring for 45min at the rotating speed of 2000r/min to finish surface treatment;
(5) carrying out filter pressing and dehydration on the calcium carbonate slurry subjected to surface treatment, wherein the solid content of a filter cake is required to be more than or equal to 55%, transferring the filter cake into an oven for drying at 120 ℃ for 36h, and crushing and grading after drying to obtain the calcium carbonate slurry with the specific surface area of 9.84m2Per gram of activated calcium carbonate.
Comparative example
(1) Crushing limestone to 2-3 cm of block size by using a jaw crusher, calcining at 1100 ℃ for 400min to obtain quicklime, carrying out digestion reaction on the quicklime and water according to the mass ratio of 1:11 of the greywater to obtain lime slurry, sieving the lime slurry by using a 100-mesh sieve to remove waste residues, adjusting the solid content of the lime slurry to 10.5%, aging the lime slurry and standing for 48 h;
(2) transferring the calcium carbonate suspension liquid obtained in the step (1) into a carbonation reaction tank with a heat-preservation jacket, adding 2.0% sodium hydroxide based on the dry calcium hydroxide, heating the calcium carbonate suspension liquid to 80 ℃, starting stirring, adjusting the stirring speed to be 100r/min, and stirring for 60min to obtain the calcium carbonate suspension liquid
(3) Conveying the calcium carbonate suspension obtained in the step (2) to a treatment barrel, heating until the temperature of slurry is 60-65 ℃, adding a sodium stearate treatment agent with the mass of 2.0 percent of the dry basis mass of calcium carbonate for surface treatment modification, and continuously stirring for 45min at the rotating speed of 1500r/min to finish surface treatment;
(4) carrying out filter pressing and dehydration on the calcium carbonate slurry subjected to surface treatment, wherein the solid content of a filter cake is required to be more than or equal to 55%, transferring the filter cake into an oven to be dried for 24 hours at 115 ℃, and crushing and grading the dried filter cake to obtain the calcium carbonate slurry with the specific surface area of 17.66m2Per gram of activated calcium carbonate.
The active calcium carbonate prepared by the invention is applied to filling a two-component silicone sealant, 107 glue, the active calcium carbonate and the silicone oil of examples 1-4 and comparative example 1 are respectively added into a power mixer to be mixed for 60min at a high speed in vacuum to prepare a component A, the material temperature is controlled to be 110-120 ℃, and the vacuum degree is-0.095 Mpa; then putting the black color paste, the curing agent, the gamma-aminopropyl triethoxysilane and the dibutyltin dilaurate into a dynamic mixing base for vacuum mixing for 20min to prepare a component B; and finally, putting the component A and the component B into a power mixer according to the mass ratio of 16:1, and mixing at a vacuum medium speed for 10min to prepare the two-component silicone adhesive. The product was formulated using a two-component silicone sealant as shown in table 1.
Table 1: two-component silicone sealant formula
The prepared two-component silicone sealant has the advantages that the fluidity, the thixotropy and the mechanical property test adopt GB 16776-.
Table 2: the performance test result of the application of the active calcium carbonate in the two-component silicone sealant
From the test results, the active calcium carbonate prepared by the invention can endow the sealant with excellent fluidity, thixotropy and mechanical properties after being filled in the two-component silicone sealant.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (10)
1. A preparation method of activated calcium carbonate for high-filling-amount bi-component silicone adhesive is characterized by comprising the following steps: the method comprises the following steps:
calcining limestone at 1100-1300 ℃ for 300-500 min to obtain quicklime, carrying out digestion reaction on the quicklime and water to obtain lime slurry, sieving the lime slurry with a 100-mesh sieve to remove waste residues, and adjusting the solid content of the lime slurry to 10-13% for later use;
feeding the lime slurry obtained in the step (1) into a carbonation reaction tower, starting a refrigeration cycle, adjusting the temperature of the lime slurry to 25-30 ℃, adding sucrose accounting for 0.01mt% of the mass of the lime slurry, introducing lime kiln recycle gas to start carbonation reaction, stopping introducing gas when the pH of a reaction system is 7.5, and stopping carbonation reaction to obtain a calcium carbonate suspension;
transferring the calcium carbonate suspension to a carbonation reaction tank containing a heat-preservation jacket, adding a morphology modifier compounded by sodium salt and saccharides, wherein the addition amount of the morphology modifier is 0.5-2.0% of the dry mass of calcium carbonate, controlling the temperature of the suspension to be 55-70 ℃, starting low-speed stirring, introducing low-concentration carbon dioxide gas within 30-90 min, and uniformly adding 5-10% of lime slurry based on the mass of the calcium carbonate suspension to obtain a large-particle-size cubic calcium carbonate suspension;
conveying the calcium carbonate suspension obtained in the step (3) to a treatment barrel, heating until the temperature of slurry is 55-70 ℃, adding a sodium stearate treatment agent accounting for 1.5-3.0% of the dry mass of calcium carbonate to perform surface treatment modification, and continuously stirring for 30-60 min to complete surface treatment;
dehydrating, drying and crushing the calcium carbonate slurry subjected to surface treatment to obtain the calcium carbonate slurry with the specific surface area of 7-12 m2Per gram of activated calcium carbonate.
2. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the digestion reaction quicklime and water are mixed according to the mass ratio of lime to water of 1: 8-12, carrying out digestion reaction.
3. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the volume concentration of carbon dioxide in the lime kiln recovered gas in the step (2) is 30-35%, and the specific surface area of the calcium carbonate suspension is 20-25 m2Between/g.
4. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the sodium salt in the step (3) comprises one or more of sodium phosphate, sodium acetate and sodium oxalate.
5. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the saccharides in the step (3) comprise glucose and/or sucrose.
6. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the mass ratio of the sodium salt to the saccharide is 3-1: 1.
7. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: and (3) the low-concentration carbon dioxide gas is tail gas recovered from the carbonation reaction tower, and the volume concentration of the low-concentration carbon dioxide gas is 5-15%.
8. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the stirring rotation speed of the steps (2) and (4) is 1000-3000r/min, and the stirring rotation speed of the step (3) is 100-150 r/min.
9. The method of preparing the activated calcium carbonate for high loading two-component silicone adhesive according to claim 1, wherein: the drying is carried out for 24-48 h at the temperature of 110-125 ℃.
10. Process for the preparation of activated calcium carbonate for high loading two-component silicone adhesives according to any of claims 1 to 9, characterized in that: the active calcium carbonate is used for filling bi-component silicone adhesive.
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| CN112374520A (en) * | 2020-11-27 | 2021-02-19 | 广西华纳新材料科技有限公司 | Preparation method of active calcium carbonate for moisture-curing polyurethane sealant |
| CN115849425A (en) * | 2022-12-09 | 2023-03-28 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of nano calcium carbonate for low-modulus high-elasticity silicone adhesive |
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