CN108148451B - Composite surface treating agent and preparation method of nano calcium carbonate for high-strength low-modulus silicone adhesive - Google Patents
Composite surface treating agent and preparation method of nano calcium carbonate for high-strength low-modulus silicone adhesive Download PDFInfo
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Abstract
The invention discloses a composite surface treating agent and a preparation method of nano calcium carbonate for high-strength low-modulus silicone adhesive, relating to the technical field of nano calcium carbonate preparation, wherein the composite surface treating agent is prepared by compounding a surfactant, simethicone, fatty acid, sodium hydroxide, tallow oil and a silane coupling agent; the preparation method of the nano calcium carbonate for the high-strength low-modulus silicone adhesive comprises the working procedures of calcining, digesting, filtering, cooling, primary carbonizing, aging, secondary carbonizing, surface treating, filter pressing, dehydrating, drying, crushing and the like of lime to obtain the product of the invention. The nano calcium carbonate prepared by the method has the particle size of 20-30 nm, is spherical, has good dispersibility and low oil absorption value, is applied to the preparation of the silicone adhesive, reduces the modulus of the silicone adhesive, obviously enhances the tensile strength of the silicone adhesive, and improves the elongation at break of the silicone adhesive material.
Description
Technical Field
The invention relates to the technical field of nano calcium carbonate preparation, in particular to a composite surface treating agent and a preparation method of nano calcium carbonate for high-strength low-modulus silicone adhesive.
Background
The nanometer calcium carbonate is used as a novel functional inorganic material, has the quantum size effect, small size effect, surface effect and macroscopic quantum effect which are not possessed by common inorganic fillers due to the superfine particle size and high specific surface area, and is widely applied to rubber plastics, coating ink, papermaking, silicone sealant and other industries due to stable performance, easy processing and low price. However, the surface of the nano calcium carbonate which is not subjected to surface modification is hydrophilic and oleophobic, and is difficult to be uniformly dispersed in the composite material; the defects of large specific surface area, high surface energy and easy inter-particle agglomeration restrict the use of the nano-carbonic acid in industry, so that the surface modification of the nano-calcium carbonate is imperative.
Silicone gel is a paste-like material that cures to a tough, rubbery solid upon exposure to air moisture. Mainly classified into deacetylated type, dealcoholized type and deaminated type. One-component silicone glass cement is a paste-like material that cures to a tough, rubbery solid upon exposure to air moisture. The silicone adhesive has the remarkable characteristics of high and low temperature resistance, weather aging resistance, ozone resistance and the like, and also has the characteristics of good adhesion to various substrates, strong displacement resistance and the like, so that the silicone adhesive becomes a key and unique structural adhesive sealing material for the hidden frame curtain wall.
The superfine calcium carbonate used in the existing silicone structural adhesive has low oil absorption value, and the prepared silicone adhesive has low viscosity, poor toughness, low tensile strength and easy sagging, and can only be used as a low-grade product. The nano calcium carbonate particles can be used as a reinforcing agent of the silicone adhesive by unique characteristics, but in the prior art, the nano calcium carbonate with the particle size of 60-90 nm is applied to the silicone adhesive, particularly to the structural silicone adhesive, the bonding strength of the nano calcium carbonate particles cannot meet the requirement, and the effect is poor. The nano calcium carbonate with the particle size of 40-60 nm is used in the silicone adhesive, although the bonding strength can meet the requirement, the dispersibility of the nano calcium carbonate is not good, particles exist on the surface of the silicone adhesive, and the cured silicone adhesive has the defects of high hardness and poor elasticity. Meanwhile, the surface of the nano calcium carbonate has poor appearance and is difficult to uniformly disperse in the composite material, so that the effect of the nano calcium carbonate applied to the silicone adhesive is not obvious.
Chinese patent CN103665937B discloses a preparation method of nano calcium carbonate special for medium-high grade silicone sealant, which comprises the procedures of size mixing, carbonization, primary surface treatment, secondary surface treatment, dehydration and drying, wherein the primary surface treatment is carried out by KH-550 or KH-560 or a mixture of the two in any proportion, and the secondary surface treatment is carried out by saponification liquid of fatty acid. The method comprises the steps of directly introducing kiln gas into a reaction kettle to carry out carbonization reaction, wherein the volume content of carbon dioxide is 25-35%, the direct introduction of kiln gas to carry out carbonization reaction causes insufficient contact between the carbon dioxide and reaction slurry, and the concentration of the carbon dioxide in the kiln gas is low, so that the carbonization reaction is slow, the reaction is not thorough, and the nucleation of nano calcium carbonate is slow; in addition, the patent adopts secondary surface treatment, so that not only the process is complicated, but also the surface treatment effect is general, so that the dispersibility of the nano calcium carbonate is poor.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the preparation method of the composite surface treating agent and the nano calcium carbonate for the high-strength low-modulus silicone adhesive is provided, and the nano calcium carbonate prepared by the method has good reinforcing performance, tensile property and lower modulus.
The technical solution of the invention is as follows:
a preparation method of the composite surface treating agent comprises the following steps:
(1) adding a surfactant into water, soaking, stirring and mixing, slowly adding dimethyl silicon oil dropwise after the surfactant is completely dissolved to obtain a mixed solution, putting the mixed solution into a high-speed dispersion emulsifying machine, and rotating at a rotating speed of 1500-2500 r/min to disperse the dimethyl silicon oil into the surfactant solution to form a homogeneous silicone oil emulsion;
(2) mixing stearic acid, sodium hydroxide and Chinese tallow tree oil, and performing saponification reaction at the reaction temperature of 50-90 ℃ to obtain homogeneous saponification liquid;
(3) and (3) mixing the homogeneous-phase silicone oil emulsion prepared in the step (1), the homogeneous-phase saponification liquid prepared in the step (2) and a silane coupling agent, putting the mixture into a high-speed dispersion emulsifying machine, rotating at the rotating speed of 1500-2500 r/min, and uniformly mixing to form the composite surface treating agent.
Preferably, in step (1), the surfactant is Triton X-100 or RHJ-01 dimethicone emulsifier.
Preferably, in the step (1), the mass ratio of the surfactant to the water is 1: 10-20, and the adding amount of the dimethyl silicone oil is 0.5-4% of the total mass of the surfactant and the water.
Preferably, in the step (2), the mass ratio of stearic acid, sodium hydroxide and Chinese tallow is 6:1: 4.
Preferably, in the step (3), the mass ratio of the homogeneous phase silicone oil emulsion to the homogeneous phase saponified solution is 1: 4-5.
Preferably, in the step (3), the silane coupling agent is KH-550, and the adding amount of the silane coupling agent is 1/1000-1/800 of the total mass of the homogeneous phase silicone oil emulsion and the homogeneous phase saponification liquid.
The method for preparing the nano calcium carbonate for the high-strength low-modulus silicone adhesive by adopting the composite surface treating agent comprises the following steps:
(1) calcining lime, and keeping the calcined lime to have the whiteness of more than 95%;
(2) selecting lime particles with the whiteness of more than 95% by a color selector, carrying out digestion reaction with water to obtain calcium hydroxide rough pulp, and sequentially passing the calcium hydroxide rough pulp through screens of 100 meshes, 200 meshes, 325 meshes and 500 meshes to obtain calcium hydroxide fine pulp;
(3) adding water into the calcium hydroxide fine pulp to adjust the mass percent concentration to be 6-8%, and cooling to the temperature of 7-10 ℃;
(4) introducing the calcium hydroxide fine slurry obtained in the step (3) into a liquid film nucleating device from a slurry inlet, and introducing pure CO from a gas inlet2Gas is introduced into the liquid film nucleator, and a crystal growth controller, pure CO, is added2The gas fully contacts with the calcium hydroxide fine slurry through a gas distributor arranged on the liquid film nucleating device to carry out carbonization reaction until the pH value of the slurry is 9-11, and then the slurry is aged for 8-12 hours;
(5) pumping the aged calcium carbonate aged slurry into a crystal grower from a slurry inlet II, and introducing 55-65 vol% CO from a gas inlet under stirring2Gas is added into a crystal grower, a crystal growth control agent is added, secondary carbonization reaction is carried out, and the reaction is carried out until the pH value of the calcium carbonate cooked slurry is 7-9, namely the carbonization end point;
(6) putting the calcium carbonate cooked slurry obtained in the step (5) into an emulsification activation reactor, and adding the composite surface treating agent to carry out surface treatment on the calcium carbonate cooked slurry for 1-2 hours;
(7) and (4) carrying out filter pressing dehydration, drying and crushing on the calcium carbonate obtained in the step (6) to obtain the high-strength and low-modulus nano calcium carbonate for the silicone adhesive.
Preferably, in the step (3), the refined calcium hydroxide slurry is subjected to heat exchange with cooling water of 7 ℃ or lower by a plate heat exchanger, so that the temperature of the refined calcium hydroxide slurry is reduced to 7 to 10 ℃.
Preferably, in the step (4), the crystal growth control agent is NaCO3。
Preferably, in the step (5), the crystal growth controller is one or a mixture of more than one of sucrose, beet sugar and maltose.
Preferably, in the step (5), the volume concentration of CO is 55-65%2The preparation method of the gas comprises the following steps: kiln gas generated by the lime kiln is dedusted by a pulse deduster and a water film deduster, then compressed by a water ring compressor into a kiln gas storage tank and stored with pure CO in the compression storage tank2Distributing gas to obtain CO with the volume concentration of 55-65%2A gas.
Preferably, in the step (6), the addition amount of the composite surface treating agent is 4-8% of the mass of the calcium carbonate cooked slurry.
Preferably, the emulsion activation reactor in the step (6) is an emulsion nucleator which is a special device developed by the applicant, and the special device is patented and has the patent number Z L201520562639.9.
The invention has the following beneficial effects:
(1) the composite surface treating agent is prepared by compounding multiple components of dimethyl silicone oil, a surfactant, saponification liquid of stearic acid tallow and a silane coupling agent, and in order to enable the dimethyl silicone oil to be dissolved in the saponification liquid of stearic acid tallow and the silane coupling agent and enable the components of the composite surface treating agent to be uniformly mixed and to play a role, the invention adopts the surfactant to carry out emulsification treatment on the dimethyl silicone oil and reduces the interfacial tension of the dimethyl silicone oil, thereby improving the solubility of the saponification liquid of the dimethyl silicone oil and the stearic acid tallow and the silane coupling agent, and simultaneously improving the stability of the composite surface treating agent, thereby playing a role in surface treatment. The composite surface treating agent has the following effects that firstly, the dimethyl silicone oil can be coated on the surface of the nano calcium carbonate, so that the modified nano calcium carbonate has oleophylic and hydrophobic properties; secondly, calcium ions on the surface of the nano calcium carbonate can chemically react with hydrophilic groups such as hydroxyl and carboxyl in saponification liquid of the tallow stearate, so that the surface of the nano calcium carbonate is changed from hydrophilic oleophobic to oleophilic hydrophobic, the active part of the surface of the nano calcium carbonate can be adsorbed on fatty acid salt by ionic bonds, fatty acid calcium is generated by precipitation reaction, a film is gradually formed on the surface of the nano calcium carbonate, the distance between calcium carbonate particles is gradually increased, and the phenomena of intermolecular interaction and particle agglomeration are reduced; the main components of the tallow oil are glyceride of oleic acid, linoleic acid and linolenic acid, and the tallow oil contains a small amount of 2, 4-decadienoic acid and palmitic acid, and contains a large amount of hydrophilic groups, so that the saponification liquid formed by the tallow oil and stearic acid has good surface treatment performance on the nano calcium carbonate. Finally, the polar group at one end of the silane coupling agent can react with the functional group on the surface of the nano calcium carbonate to form a stable chemical bond. Therefore, the invention adopts the mutual cooperation and mutual cooperation of the saponification liquid of the dimethyl silicone oil and the stearic acid tallow and the silane coupling agent to form the composite surface treating agent, has good surface treating effect and greatly improves the surface treating performance of the nano calcium carbonate.
(2) The composite surface treating agent is used for carrying out surface treatment on the nano calcium carbonate, so that the surface activity of the nano calcium carbonate can be reduced, and the acting force among crystal grains can be reduced, thereby improving the dispersibility of the nano calcium carbonate in a polymer matrix and reducing the oil absorption value; therefore, the nano calcium carbonate prepared by the preparation method has the particle size of 20-30 nm, the particles are spherical, the dispersibility is good, the oil absorption value is low, the strength of the silicone adhesive composite material can be improved when the nano calcium carbonate prepared by the preparation method is applied to the preparation of the silicone adhesive, the 'rolling ball effect' is formed due to the spherical nano calcium carbonate, the compatibility is good, the modulus of the silicone adhesive is reduced, the tensile strength of the silicone adhesive is obviously enhanced, and the elongation at break of the silicone adhesive material is improved; and the defect of poor performance when being applied to silicone adhesive caused by poor dispersity of the nano calcium carbonate with small particle size in the prior art is overcome.
Drawings
FIG. 1 is a schematic view of the structure of a carbonization reactor according to the present invention;
shown in the figure: 1. a liquid film nucleator; 11. a pulp inlet I; 12. a first gas inlet; 13. a gas distributor; 14. a first slurry outlet; 2. a crystal grower; 21. a second pulp inlet; 22. a second gas inlet; 23. a second pulp outlet; 24. a stirrer; 25. a motor; 3. and (4) a pump.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example one
The carbonization reactor of the invention as shown in fig. 1 comprises a liquid film nucleating device 1 and a crystal grower 2, wherein the upper end of the liquid film nucleating device 1 is provided with a slurry inlet I11 and a slurry outlet I14, the lower end is provided with a gas inlet I12, the slurry inlet I11 and the slurry outlet I14 are respectively positioned at two sides of the liquid film nucleating device 1, and the liquid film nucleating device 1 is also internally provided with a gas distributor 13; the upper end of the crystal grower 2 is provided with a slurry inlet II 21, the lower end of the crystal grower 2 is provided with a gas inlet II 22 and a slurry outlet II 23, the crystal grower 2 is internally provided with a stirrer 24, the outside of the crystal grower 2 is provided with a motor 25 connected with the stirrer 24, the slurry outlet I14 is communicated with the slurry inlet II 21 through a pump 3, the slurry inlet I, the slurry inlet II, the gas inlet I and the gas inlet II are respectively provided with a flow regulating valve (not marked in figure 1) for controlling the flow of slurry and gas, and the liquid film nucleating device 1 and the crystal grower 2 are fixed on the ground through a support column (not marked in figure 1).
A preparation method of the composite surface treating agent comprises the following steps:
(1) adding triton X-100 into water for soaking, stirring and mixing, wherein the mass ratio of the triton X-100 to the water is 1:10, slowly dropwise adding dimethyl silicone oil after the triton X-100 is completely dissolved, wherein the adding amount of the methyl silicone oil is 0.5 percent of the total mass of the surfactant and the water to obtain a mixed solution, and putting the mixed solution into a high-speed dispersion emulsifying machine to rotate at the rotating speed of 1500r/min so that the dimethyl silicone oil is dispersed into the surfactant solution to form a uniform phase silicone oil emulsion;
(2) mixing stearic acid, sodium hydroxide and Chinese tallow tree oil according to the mass ratio of 6:1:4, and carrying out saponification reaction at the reaction temperature of 50 ℃ to obtain homogeneous saponification liquid;
(3) and (2) mixing the homogeneous-phase silicone oil emulsion prepared in the step (1), the homogeneous-phase saponified liquid prepared in the step (2) and KH-550, wherein the mass ratio of the homogeneous-phase silicone oil emulsion to the homogeneous-phase saponified liquid is 1:4, the adding amount of the silane coupling agent is 1/1000 of the total mass of the homogeneous-phase silicone oil emulsion and the homogeneous-phase saponified liquid, and putting the mixture into a high-speed dispersion emulsifying machine to rotate at the rotating speed of 1500r/min for uniform mixing, so that the composite surface treating agent is formed.
The method for preparing the nano calcium carbonate by adopting the composite surface treating agent comprises the following steps:
(1) calcining lime, wherein the lime needs to be partially calcined in the calcining process, so that the whiteness of the calcined lime is over 95 percent;
(2) selecting lime particles with whiteness of more than 95% by a color selector, adding the lime particles into a slaker, adding water for slaking reaction to obtain calcium hydroxide rough pulp, and sequentially sieving the calcium hydroxide rough pulp by screens of 100 meshes, 200 meshes, 325 meshes and 500 meshes to obtain calcium hydroxide fine pulp;
(3) adding water into the calcium hydroxide refined slurry to adjust the mass percentage concentration to be 7%, and exchanging heat with cooling water below 7 ℃ through a plate heat exchanger to reduce the temperature of the calcium hydroxide refined slurry to 8 ℃;
(4) kiln gas generated by the lime kiln is dedusted by a pulse deduster and a water film deduster, then compressed by a water ring compressor into a kiln gas storage tank and stored with pure CO in the compression storage tank2Gas is distributed to obtain CO with the volume concentration of 60 percent2A gas;
(5) introducing the calcium hydroxide fine slurry obtained in the step (3) into a liquid film nucleating device from a slurry inlet, and introducing pure CO from a gas inlet2Gas is introduced into the liquid film nucleator, and a crystal growth controller, pure CO, is added2Gas is fully contacted with calcium hydroxide slurry through a gas distributor arranged on the liquid film nucleating device to carry out carbonization reaction at the temperature of 20 ℃ to obtain CaCO3Crystal nucleus liquid;
(6) to be carbonized to CaCO3When the pH of the crystal nucleus liquid is 10, CaCO is added3Introducing the crystal nucleus liquid into an aging tank for aging for 10 hours;
(7) aging CaCO3Pumping the crystal nucleus liquid into the crystal grower from the slurry inlet II, and introducing 60 volume percent CO from the gas inlet II under stirring2Gas is put into a crystal grower, a crystal growth control agent is added, secondary carbonization reaction is carried out, and the reaction is carried out until the pH value of the calcium carbonate mature slurry is 8, namely the carbonization end point;
(8) putting the calcium carbonate cooked pulp into an emulsification activation reactor, adding the composite surface treating agent to carry out surface treatment on the calcium carbonate cooked pulp for 1h, wherein the adding amount of the composite surface treating agent is 4% of the mass of the calcium carbonate cooked pulp;
(9) and (3) carrying out filter pressing dehydration, drying by a belt dryer, grading by a mill powder grader and packaging to obtain the nano calcium carbonate with high dispersibility and low oil absorption value.
Example two
A preparation method of the composite surface treating agent comprises the following steps:
(1) adding an RHJ-01 dimethyl silicone oil emulsifier into water for soaking, stirring and mixing, wherein the mass ratio of the triton X-100 to the water is 1:15, slowly dropwise adding dimethyl silicone oil after the triton X-100 is completely dissolved, wherein the adding amount of the methyl silicone oil is 2% of the total mass of the surfactant and the water to obtain a mixed solution, and putting the mixed solution into a high-speed dispersion emulsifying machine to rotate at the rotating speed of 2000r/min so that the dimethyl silicone oil is dispersed into a surfactant solution to form a homogeneous phase silicone oil emulsion;
(2) mixing stearic acid, sodium hydroxide and Chinese tallow tree oil according to the mass ratio of 6:1:4, and carrying out saponification reaction at the reaction temperature of 70 ℃ to obtain homogeneous saponification liquid;
(3) and (2) mixing the homogeneous phase silicone oil emulsion prepared in the step (1), the homogeneous phase saponified liquid prepared in the step (2) and KH-550, wherein the mass ratio of the homogeneous phase silicone oil emulsion to the homogeneous phase saponified liquid is 1:4.5, the adding amount of the silane coupling agent is 1/900 of the total mass of the homogeneous phase silicone oil emulsion and the homogeneous phase saponified liquid, and putting the mixture into a high-speed dispersion emulsifying machine to rotate and mix uniformly at the rotating speed of 2000r/min to form the composite surface treating agent.
The method for preparing nano calcium carbonate by using the composite surface treating agent is the same as the first embodiment except that the adding amount of the composite surface treating agent in the step (8) is 6 percent of the mass of the calcium carbonate cooked slurry, and the surface treatment is carried out for 1.5 hours.
EXAMPLE III
A preparation method of the composite surface treating agent comprises the following steps:
(1) adding triton X-100 into water for soaking, stirring and mixing, wherein the mass ratio of the triton X-100 to the water is 1:20, slowly dropwise adding dimethyl silicone oil after the triton X-100 is completely dissolved, wherein the adding amount of the methyl silicone oil is 4% of the total mass of the surfactant and the water to obtain a mixed solution, and putting the mixed solution into a high-speed dispersion emulsifying machine to rotate at the rotating speed of 2500r/min so that the dimethyl silicone oil is dispersed into a surfactant solution to form a homogeneous phase silicone oil emulsion;
(2) mixing stearic acid, sodium hydroxide and Chinese tallow tree oil according to the mass ratio of 6:1:4, and carrying out saponification reaction at the reaction temperature of 90 ℃ to obtain homogeneous saponification liquid;
(3) and (2) mixing the homogeneous-phase silicone oil emulsion prepared in the step (1), the homogeneous-phase saponified liquid prepared in the step (2) and KH-550, wherein the mass ratio of the homogeneous-phase silicone oil emulsion to the homogeneous-phase saponified liquid is 1:5, the adding amount of the silane coupling agent is 1/1000 of the total mass of the homogeneous-phase silicone oil emulsion and the homogeneous-phase saponified liquid, and putting the mixture into a high-speed dispersion emulsifying machine to rotate and mix uniformly at the rotating speed of 2500r/min to form the composite surface treating agent.
The method for preparing nano calcium carbonate by using the composite surface treating agent is the same as the first embodiment except that the adding amount of the composite surface treating agent in the step (8) is 8 percent of the mass of the calcium carbonate cooked slurry, and the surface treatment is carried out for 2 hours.
Comparative example 1
A method for preparing nano calcium carbonate comprises the following steps: the preparation method is the same as the first example, except that KH-550 is adopted to carry out surface treatment on the calcium carbonate cooked pulp for 1 hour in the step (8), and the adding amount of the KH-550 is 4 percent of the mass of the calcium carbonate cooked pulp.
Comparative example No. two
A method for preparing nano calcium carbonate comprises the following steps: the preparation method is the same as the first embodiment except that the step (8) is changed to adopt saponification liquid obtained by reacting stearic acid, sodium hydroxide and Chinese tallow in a mass ratio of 6:1:4 to perform surface treatment on the calcium carbonate cooked pulp for 1 hour, and the addition amount of the saponification liquid is 4 percent of the mass of the calcium carbonate cooked pulp.
Application test of nano calcium carbonate prepared in examples and comparative examples:
the nano calcium carbonate products prepared in the examples and the comparative examples are applied to the filling of silicone sealant, and are prepared according to the following formula and method:
the formula is as follows:
107 Room temperature vulcanized Silicone rubber (manufactured by Dow Corning Co., Ltd.) 210g
30g of dimethicone (manufactured by Dow Corning Co., Ltd.)
Organosilicon crosslinking agent (produced by Hubei New blue sky Material Co., Ltd.) 33g
Silane coupling agent (produced by Jiangsu morning light coupling agent Co., Ltd.) 2g
0.5g of catalyst (manufactured by Beijing Zhengheng chemical Co., Ltd.)
360g of nano calcium carbonate (prepared in examples one to three and comparative examples one to two)
The preparation method comprises the following steps: adding room temperature vulcanized silicone rubber, dimethyl silicone oil and nano calcium carbonate into a kneader according to the proportion, performing vacuum dehydration and stirring for 3.5 hours at the temperature of 140-150 ℃, adding the materials into a planetary stirrer when the materials are naturally cooled to the room temperature, sequentially adding the organosilicon crosslinking agent, the coupling agent and the catalyst according to the proportion, performing vacuum stirring for 1 hour, discharging, and filling into a sealed rubber cylinder for storage to obtain the silicone adhesive. The performance of the alloy is tested according to the national standard GB/T14683-2003, and the result is as follows:
the tensile modulus and elongation of the silicone adhesive were tested according to GB/T13477.8-2002, and the test results are as follows:
it can be seen from the above table that the nano calcium carbonate prepared in the first to third examples is applied to the silicone adhesive, and the performance of the obtained silicone adhesive is not only superior to the national standard, but also significantly superior to the performance of the comparative example applied to the silicone adhesive, especially the tensile strength and the elongation at break are significantly superior to the comparative example, so that the nano calcium carbonate prepared by the invention can be applied to the silicone adhesive to improve the strength of the silicone adhesive and reduce the modulus of the silicone adhesive.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of the composite surface treating agent is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a surfactant into water, soaking, stirring and mixing, slowly adding dimethyl silicon oil dropwise after the surfactant is completely dissolved to obtain a mixed solution, putting the mixed solution into a high-speed dispersion emulsifying machine, and rotating at a rotating speed of 1500-2500 r/min to disperse the dimethyl silicon oil into the surfactant solution to form a homogeneous silicone oil emulsion;
(2) mixing stearic acid, sodium hydroxide and Chinese tallow tree oil, and performing saponification reaction at 50-90 ℃ to obtain homogeneous saponification liquid;
(3) mixing the homogeneous-phase silicone oil emulsion prepared in the step (1), the homogeneous-phase saponification liquid prepared in the step (2) and a silane coupling agent, putting the mixture into a high-speed dispersion emulsifying machine, rotating at the rotating speed of 1500-2500 r/min, and uniformly mixing to form a composite surface treating agent; in the step (1), the surfactant is a triton X-100 or RHJ-01 dimethyl silicone oil emulsifier; in the step (1), the mass ratio of the surfactant to the water is 1: 10-20, and the addition amount of the dimethyl silicone oil is 0.5-4% of the total mass of the surfactant and the water.
2. The method for producing the composite surface treating agent according to claim 1, characterized in that: in the step (2), the mass ratio of stearic acid, sodium hydroxide and Chinese tallow is 6:1: 4.
3. The method for producing the composite surface treating agent according to claim 1, characterized in that: in the step (3), the mass ratio of the homogeneous phase silicone oil emulsion to the homogeneous phase saponification liquid is 1: 4-5.
4. The method for producing the composite surface treating agent according to claim 1, characterized in that: in the step (3), the silane coupling agent is KH-550, and the adding amount of the silane coupling agent is 1/1000-1/800 of the total mass of the homogeneous phase silicone oil emulsion and the homogeneous phase saponification liquid.
5. A preparation method of nano calcium carbonate for silicone adhesive is characterized by comprising the following steps: the method comprises the following steps:
(1) calcining lime, and keeping the calcined lime to have the whiteness of more than 95%;
(2) selecting lime particles with the whiteness of more than 95% by using a color selector, carrying out digestion reaction on the lime particles and water to obtain calcium hydroxide rough pulp, and sequentially passing the calcium hydroxide rough pulp through screens of 100 meshes, 200 meshes, 325 meshes and 500 meshes to obtain calcium hydroxide fine pulp;
(3) adding water into the calcium hydroxide fine pulp to adjust the mass percent concentration to be 6-8%, and cooling to the temperature of 7-10 ℃;
(4) introducing the calcium hydroxide fine slurry obtained in the step (3) into a liquid film nucleating device from a slurry inlet, and introducing pure CO from a gas inlet2Gas is introduced into the liquid film nucleator, and a crystal growth controller, pure CO, is added2The gas fully contacts with the calcium hydroxide fine slurry through a gas distributor arranged on the liquid film nucleating device to carry out carbonization reaction, and the gas is aged for 8-12 hours when the pH value of the slurry is 9-11;
(5) pumping the aged calcium carbonate aged slurry into a crystal grower from a slurry inlet II, and introducing 55-65 vol% CO from a gas inlet under stirring2Gas is added into a crystal grower, a crystal growth control agent is added, secondary carbonization reaction is carried out, and the reaction is carried out until the pH value of the calcium carbonate cooked slurry is 7-9, namely the carbonization end point;
(6) putting the calcium carbonate cooked slurry obtained in the step (5) into an emulsification activation reactor, and adding the composite surface treatment agent prepared in the step (3) in the claim 1 to perform surface treatment on the calcium carbonate cooked slurry for 1-2 hours;
(7) and (4) carrying out filter pressing dehydration, drying and crushing on the calcium carbonate obtained in the step (6) to obtain the nano calcium carbonate for the silicone adhesive.
6. The method for preparing nano calcium carbonate for silicone adhesive according to claim 5, wherein the method comprises the following steps: in the step (5), CO with the volume concentration of 55-65%2The preparation method of the gas comprises the following steps: kiln gas generated by the lime kiln is dedusted by a pulse deduster and a water film deduster, then compressed by a water ring compressor into a kiln gas storage tank and stored with pure CO in the compression storage tank2Distributing gas to obtain CO with the volume concentration of 55-65%2A gas.
7. The method for preparing nano calcium carbonate for silicone adhesive according to claim 5, wherein the method comprises the following steps: in the step (6), the adding amount of the composite surface treating agent is 4-8% of the mass of the calcium carbonate cooked slurry.
8. The method for preparing nano calcium carbonate for silicone adhesive according to claim 5, wherein the method comprises the following steps: in the step (3), the calcium hydroxide refined slurry exchanges heat with cooling water at a temperature below 7 ℃ through a plate heat exchanger, so that the temperature of the calcium hydroxide refined slurry is reduced to 7-10 ℃.
9. The method for preparing nano calcium carbonate for silicone adhesive according to claim 5, wherein the method comprises the following steps: in the step (4), the crystal growth control agent is NaCO3。
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