CN115197603B - Preparation method of composite calcium carbonate-titanium dioxide - Google Patents
Preparation method of composite calcium carbonate-titanium dioxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2241—Titanium dioxide
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention provides a preparation method of composite calcium carbonate-titanium dioxide, which comprises the following steps: adding a dispersing agent into the calcium carbonate slurry, and fully mixing; adding a coating agent into the titanium dioxide slurry, and rapidly and fully stirring to uniformly coat the coating agent on the surfaces of the nano titanium dioxide particles; slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, heating the calcium carbonate-titanium dioxide mixed solution, rapidly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; filtering, washing and drying the solid mixture to obtain a finished product of the calcium carbonate powder with the fine particles of the titanium dioxide uniformly adhered to the surface, and obtaining the calcium carbonate-titanium dioxide composite product. The composite material has high surface activation energy, strong chemical activity, oxidation capability and existence of hydroxyl, is suitable for being used as chemical filler in the fields of papermaking, coating and the like, and has high filling proportion and good filling effect.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of composite calcium carbonate-titanium dioxide.
Background
Nanometer titanium dioxide (TiO) 2 ) As a photocatalyst, the nano-functional material is an N-type semiconductor material with excellent performance, can fully utilize solar energy, is efficient, energy-saving and environment-friendly, has better light stability and higher reaction activity when reacting, is nontoxic and free from secondary pollution, and has the widest application prospect at present. Is widely applied to the fields of wastewater treatment, air purification, sterilization and disinfection, medical technology, environment-friendly material preparation and the like.
Calcium carbonate is used as an important inorganic chemical raw material, has the characteristics of rich resource reserves, no toxicity, no smell, excellent performance and the like, and is widely applied to the fields of paint, plastics, papermaking, rubber, printing ink and the like. Especially in the coating field, calcium carbonate is attracting more and more attention, and in the water-based coating industry, calcium carbonate can prevent the coating from sedimentation, so that the coating has good dispersibility and high glossiness, and the consumption of calcium carbonate in the water-based coating accounts for 20% -60%. In the coating, calcium carbonate plays a role of a framework, the thickness of a coating film can be increased, the wear resistance of the coating is improved, and the adhesive force of the coating is obviously improved. The calcium carbonate is added into the paint, so that the rheological property, toughness, water resistance, weather resistance and stability of the paint can be changed.
However, the existing calcium carbonate has the defects of low covering power, easy pulverization phenomenon under long-time sunlight irradiation and the like, which limits the application range of the calcium carbonate. In addition, calcium carbonate has low whiteness and cannot be used as a pigment auxiliary agent in a paint.
Patent CN101302359A provides a preparation method of composite titanium dioxide, which is characterized in that sodium silicate is used as a binder and a coating agent, and titanium dioxide particles are embedded on the surface of light calcium carbonate. The method realizes the stepwise completion of the coating of the calcium carbonate and the coating of the titanium dioxide in the carbonation reaction process, but the method has larger amount of the titanium dioxide added, improves the production cost, has complex technical operation process and has a certain difficulty in realizing industrialization. The patents CN1444543a and CN103897438A provide a method for preparing titanium dioxide-calcium carbonate composite particles, which is characterized in that titanium dioxide particles are directly coated on the surface of calcium carbonate through carbonization reaction, and the preparation process is that a mixture of carbon dioxide and air is introduced into calcium hydroxide slurry under stirring until the pH value of the slurry is 7. The technology for preparing the titanium dioxide-calcium carbonate composite particles by using the carbonization method is firstly proposed, so that partial coating of titanium dioxide on the surface of calcium carbonate is realized, and the whiteness of the product is improved. However, the titanium dioxide-calcium carbonate composite particles prepared by the method have the phenomena of unstable composite particles, easy stripping of titanium dioxide, low coating rate of calcium carbonate and the like. Patent CN103194089 provides a preparation method of composite titanium dioxide, which is characterized in that meta-titanic acid is used as a titanium source coating agent, sodium silicate is added as a binder and a coating agent, and the composite titanium dioxide is obtained through suction filtration, water washing, drying and crushing. The invention changes the raw material of the titanium dioxide from commercial titanium dioxide into the meta-titanic acid, reduces the production cost, completes the coating of calcium carbonate and the coating after titanium dioxide in the preparation process, but because the specific gravity difference between the titanium dioxide and the calcium carbonate is larger, the coating rate difference of the calcium carbonate in the product is also larger, the particle size of the meta-titanic acid is tens of nanometers, the meta-titanic acid is easy to agglomerate, the bonding between the meta-titanic acid particles after secondary agglomeration and the calcium carbonate is possibly not firm enough, and the required drying temperature is higher and the time is longer. In addition, the process of preparing the picnic acid by the sulfuric acid method can cause a certain pollution to the environment.
Disclosure of Invention
The invention aims to provide a preparation method of composite calcium carbonate-titanium dioxide, which aims to solve at least one of the technical problems in the prior art.
In order to solve the technical problems, the preparation method of the composite calcium carbonate-titanium dioxide provided by the invention comprises the following steps:
s10, adding a dispersing agent into calcium carbonate slurry, and fully mixing to obtain calcium carbonate mixed solution with uniformly dispersed calcium carbonate;
s20, adding a coating agent into the titanium dioxide slurry, and rapidly and fully stirring to uniformly coat the coating agent on the surfaces of the nano titanium dioxide particles to obtain uniformly dispersed titanium dioxide mixed solution;
s30, slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, and keeping stirring during the period to ensure that the mixed solution does not settle and is fully and uniformly mixed to obtain the calcium carbonate-titanium dioxide mixed solution;
s40, heating the calcium carbonate-titanium dioxide mixed solution, rapidly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; filtering, washing and drying the solid mixture to obtain a finished product of the calcium carbonate powder with the fine particles of the titanium dioxide uniformly adhered to the surface, and obtaining the calcium carbonate-titanium dioxide composite product.
Further, in the step S10, the calcium carbonate slurry is light calcium carbonate slurry with the concentration of 6% -15%; in the step S10, the addition amount of the dispersing agent is 0.5-1.5% of the dry weight of the light calcium silicate.
Further, in step S20, the concentration of the titanium dioxide slurry is 15% -20%.
Further, in the step S20, the addition amount of the coating agent is 1.5% -2.0% of the weight of the dry basis of the nano titanium dioxide.
Further, the dispersant in the step S10 is a mixed solution obtained by mixing 0.5% -2.5% of isobutanol solution and 0.9% -2.8% of 2-ethylhexanol solution; the molar ratio of the isobutanol to the 2-ethylhexanol in the mixed solution is 1:1-1:2.
Further, in the step S20, the coating agent is a mixed solution obtained by mixing a vinyl alcohol solution with the mass concentration of 0.2% -1.0% and an acrylic acid solution with the mass concentration of 0.5% -1.2%, and the molar ratio of the vinyl alcohol to the acrylic acid in the mixed solution is 2:1-1:1.
Further, in step S30, the mixing ratio of the titanium dioxide mixed solution and the calcium carbonate mixed solution satisfies the condition that the mass ratio of the dry-based titanium dioxide to the dry-based calcium carbonate is 0.1-0.15.
Further, in the step S40, the heating temperature is 65-85 ℃, the stirring rotation speed is 350-600 r/min, and the mixing time is 15-40 min.
Further, after the full reaction in the step S40, (without cooling), solid-liquid separation and washing are immediately carried out, the solid after the solid-liquid separation is collected, spraying washing is carried out by using hot water with the volume of 1.5-2 times, and the temperature of the hot water is 45-55 ℃.
Preferably, in step S10, ultrasonic agitation mixing is employed.
When the light calcium carbonate is used as a matrix, the crystal form of the light calcium carbonate is calcite, the microscopic form is spindle-shaped, the light calcium carbonate has the characteristics of higher whiteness, stronger covering power, strong weather resistance and the like, the nano-grade titanium dioxide is compounded on the surface of the matrix, the titanium dioxide is uniformly coated on the surface of the matrix, the coating rate is high, the binding property is good, the surface activation energy of the composite material is high, the strong chemical activity, the oxidation capability and the existence of hydroxyl exist, and the light calcium carbonate is suitable for being used as chemical filler in the fields of papermaking, coating and the like, and the filling proportion is high, and the filling effect is good.
And the invention uses isobutanol and 2-ethylhexanol as dispersing agents of light calcium carbonate, uses vinyl alcohol and acrylic acid as coating agents of nano titanium dioxide, replaces assistants such as sodium silicate, meta-titanic acid and the like in the prior art, has simple process implementation, good dispersing and coating effects, and tightly combines titanium dioxide and matrix light calcium carbonate, and has no toxicity and harm to various raw materials in the production process, thus playing a certain role in protecting environmental resources.
Finally, the nano-scale titanium dioxide and the light calcium carbonate are combined in a heating and high-speed stirring system, and finally the nano-scale titanium dioxide fine particles are attached on the surface structure of the light calcium carbonate, so that the combination strength of the light calcium carbonate and the titanium dioxide is far higher than that of the traditional composite modification.
Further, in step S10, the calcium carbonate slurry is hydrated calcium silicate slurry with the concentration of 9% -15%;
in the step S10, the addition amount of the dispersing agent is 2.0-3.5% of the dry weight of the hydrated calcium silicate.
Further, in the step S20, the concentration of the titanium dioxide slurry is 21% -35%; the addition amount of the coating agent is 2.1-3.0% of the weight of the dry basis of the nano titanium dioxide.
Further, in the step S10, the dispersant is a mixed solution of a sodium pyrophosphate solution and an ethanol solution of diethyl phthalate; wherein, the mass concentration of the sodium pyrophosphate solution is 12.5-18.5%; the mass concentration of the ethanol solution of diethyl phthalate is 8.0% -11.5%; the molar ratio of the sodium pyrophosphate to the diethyl phthalate in the mixed solution is 1:3-1:5.
Further, in the step S20, the coating agent is a mixed solution obtained by mixing a 6- (2, 3-dimethylmaleimide) hexyl methacrylate solution with the mass concentration of 2.5% -5.0% and a 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt solution with the mass concentration of 5.5% -10%, and the molar ratio of the 6- (2, 3-dimethylmaleimide) hexyl methacrylate to the 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt in the mixed solution is 1:2-1:4.
Further, in step S30, the mixing ratio of the titanium dioxide mixed solution and the calcium carbonate mixed solution satisfies the condition that the mass ratio of the dry-based titanium dioxide to the dry-based calcium carbonate is 0.2-0.25.
Further, in the step S40, the heating temperature is 88 ℃ to 95 ℃, the stirring rotation speed is 650r/min to 1200r/min, and the mixing time is 50min to 90min.
Further, after the full reaction in the step S40, solid-liquid separation and washing are immediately carried out (without cooling), the solid after the solid-liquid separation is collected, and hot water with the volume of 3.5-4 times is used for spray washing, wherein the temperature of the hot water is 60-75 ℃.
When the hydrated calcium silicate is used as a matrix, the hydrated calcium silicate is amorphous in crystal form and honeycomb in porous structure in microscopic form, and the calcium silicate has the characteristics of higher whiteness, stronger covering power, strong weather resistance and the like.
And sodium pyrophosphate and diethyl phthalate are used as dispersing agents of hydrated calcium silicate, 6- (2, 3-dimethyl maleimide) hexyl methacrylate and 4- (N-maleimide methyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt are used as coating agents of the nano titanium dioxide, and the nano titanium dioxide coating agent replaces assistants such as sodium silicate, meta-titanic acid and the like in the prior art, has simple process implementation, good dispersing and coating effects, and the titanium dioxide and the matrix hydrated calcium silicate are tightly combined, and various raw materials are nontoxic and harmless in the production process, so that the nano titanium dioxide coating agent has a certain protection effect on environmental resources.
Finally, the nano-scale titanium dioxide and the hydrated calcium silicate are combined in a heating and high-speed stirring system, and finally the nano-scale titanium dioxide fine particles are attached on the surface structure of the hydrated calcium silicate, so that the combination strength of the hydrated calcium silicate and the titanium dioxide is far higher than that of the traditional composite modification.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the invention and that other drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a calcium carbonate-titanium dioxide composite material prepared in example 2 of the present invention;
FIG. 2 is a scanning electron microscope image of the calcium carbonate-titanium pigment composite material prepared in example 4 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further illustrated with reference to specific embodiments.
Example 1
The embodiment discloses a preparation method of composite calcium carbonate-titanium dioxide, which comprises the following steps:
1) 20g of isobutanol solution with the mass concentration of 0.5% and 17.57g of 2-ethylhexanol solution with the mass concentration of 1.0% are mixed to prepare a dispersing agent for standby, wherein the mol ratio of isobutanol to 2-ethylhexanol is 1:1;
2) 10g of a vinyl alcohol solution with the mass concentration of 0.7% and 11.45g of an acrylic acid solution with the mass concentration of 1.0% are mixed to prepare a coating agent for standby, wherein the molar ratio of the vinyl alcohol to the acrylic acid is 1:1;
3) Taking 5kg of light calcium carbonate slurry with the mass concentration of 10%, adding 5g of the prepared dispersing agent, and carrying out ultrasonic vibration mixing to prepare calcium carbonate mixed solution;
4) Taking 250g of titanium dioxide slurry with the mass concentration of 20%, adding 1g of the prepared coating agent, and stirring at a high speed to prepare a titanium dioxide mixed solution;
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring rotation speed at 350r/min during the period, keeping the mixed solution from sedimentation, heating to 75 ℃ after complete mixing, carrying out rapid stirring at 550r/min, carrying out solid-liquid separation on slurry after mixing for 30min, and then sequentially filtering and washing the mixture; wherein, the washing process uses 1.1L hot water with the temperature of 50 ℃ for spraying, and the calcium carbonate-titanium dioxide composite product is finally obtained after washing, drying and collecting.
As shown in Table 1, the ash content of the obtained pulp after being made into paper is tested, the ash content of the paper can reach 29.48%, the filler retention rate can reach 75.26%, and the ash content and the filler retention rate of the paper prepared by directly adding the GCC filler and the PCC filler as papermaking fillers are far higher than those of the paper.
In addition, the strength of the paper under the condition of the embodiment is higher than that of paper manufactured by adopting the traditional GCC and PCC as fillers.
Table 1 comparison of the process with GCC, PCC filler paper properties under the conditions of example 1
The embodiment solves the technical problems of easy agglomeration, complex production process, low calcium carbonate coating rate and the like of the nanoscale titanium dioxide in the prior art. And (3) under the conditions of a specific dispersing agent and a coating agent, carrying out viscose coating on the surfaces of titanium dioxide particles in advance, then mixing the titanium dioxide particles with light calcium carbonate slurry, and uniformly coating the titanium dioxide on the surfaces of the calcium carbonate by heating and stirring at a high speed. The technology that titanium dioxide and calcium carbonate are compounded by utilizing the dispersing agent and the coating agent in a synergistic way is provided, uniform coating of titanium dioxide on the surface of calcium carbonate is realized, the structural stability of the composite material is improved, the composite material adopts a simple and convenient process method which is easy to realize, the production process is environment-friendly and low-carbon and energy-saving, the dispersibility and weather resistance of the product are improved, the whiteness, dry and wet covering capacity and decoloring capacity of the material are improved, and the composite material is successfully used in the papermaking industry and the coating industry.
Example 2
The embodiment discloses a preparation method of composite calcium carbonate-titanium dioxide, which comprises the following steps:
1) 15.00g of isobutanol solution with the mass concentration of 1.5% and 22.73g of 2-ethylhexanol solution with the mass concentration of 2.0% are mixed to prepare a dispersing agent for standby, wherein the mol ratio of isobutanol to 2-ethylhexanol is 1:1.5;
2) 5g of a vinyl alcohol solution with the mass concentration of 0.5% and 3.41g of an acrylic acid solution with the mass concentration of 0.8% are mixed to prepare a coating agent for standby, wherein the mol ratio of the vinyl alcohol to the acrylic acid is 1.5:1;
3) Taking 10kg of light calcium carbonate slurry with the mass concentration of 10%, adding 12g of the prepared dispersing agent, and carrying out ultrasonic vibration mixing to obtain calcium carbonate mixed solution;
4) 200g of titanium dioxide slurry with the mass concentration of 18% is taken, 0.65g of the prepared coating agent is added, and high-speed stirring is carried out to obtain titanium dioxide mixed solution;
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring rotation speed at 380r/min during the period, keeping the mixed solution from sedimentation, heating to 80 ℃ after complete mixing, quickly stirring at 600r/min, carrying out solid-liquid separation on slurry after mixing for 25min, sequentially filtering and washing the mixture, spraying 1.9L of hot water at 55 ℃, drying and collecting after washing, and finally obtaining the calcium carbonate-titanium dioxide composite product.
FIG. 1 is a scanning electron microscope image of a calcium carbonate-titanium dioxide composite material prepared in this example; the comparison of the properties of the samples in this example and example 1 is shown in Table 2.
Table 2 sample performance index of example 1, 2
| Sample numbering | Whiteness (%) | Hiding power (g/m) 2 ) | Oil absorption (g/100 g) | Brightness of light | Photocatalytic Activity |
| Example 1 | 98.9 | 23.4 | 31.5 | 96.4 | 0.28 |
| Example 2 | 99.2 | 24.2 | 28.6 | 96.8 | 0.30 |
Note that: the photocatalytic activity value characterizes the weatherability of the composite material, the lower the photocatalytic activity value, the better the weatherability.
Example 3
The embodiment discloses a preparation method of composite calcium carbonate-titanium dioxide, which comprises the following steps:
1) 20g of sodium pyrophosphate solution with the mass concentration of 15% and 105.57g of diethyl phthalate ethanol solution with the mass concentration of 9.5% are mixed to prepare a dispersing agent for later use; wherein the molar ratio of sodium pyrophosphate to diethyl phthalate is 1:4.
2) 20g of 6- (2, 3-dimethylmaleimide) hexyl methacrylate solution with the mass concentration of 3% and 315g of 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt solution with the mass concentration of 8.5% are mixed to prepare a coating agent for standby, wherein the molar ratio of 6- (2, 3-dimethylmaleimide) hexyl methacrylate to 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt is 1:3.
3) Taking 5kg of hydrated calcium silicate slurry with the mass concentration of 10%, adding 12.5g of the prepared dispersing agent, and carrying out ultrasonic vibration mixing to obtain calcium carbonate mixed solution.
4) 400g of titanium dioxide slurry with the mass concentration of 25% is taken, 2.5g of the prepared coating agent is added, and high-speed stirring is carried out to obtain titanium dioxide mixed solution.
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring rotation speed at 650r/min during the period, keeping the mixed solution from sedimentation, heating to 90 ℃ after complete mixing, carrying out rapid stirring at 1100r/min, carrying out solid-liquid separation on slurry after mixing for 60min, sequentially filtering and washing the mixture, spraying 2.4L of hot water at 65 ℃ in the washing process, drying and collecting after washing, and finally obtaining the hydrated calcium silicate-titanium dioxide composite product.
Referring to Table 3, the ash content of the obtained pulp after being made into paper is tested to be 36.84%, the filler retention rate can be 82.37%, and the ash content and the filler retention rate are far higher than those of paper in which GCC filler and PCC filler are directly used as papermaking fillers and added into paper; in addition, the strength of the paper under the condition of the embodiment is higher than that of paper manufactured by adopting the traditional GCC and PCC as fillers.
TABLE 3 comparison of the process with GCC, PCC filler paper Performance under the conditions of EXAMPLE 3
The invention uses the hydrated calcium silicate as a matrix, the crystal form of the hydrated calcium silicate is amorphous, the microscopic form is a honeycomb porous structure, the invention has the characteristics of higher whiteness, stronger covering power, strong weather resistance and the like, the surface of the matrix is compounded with the nano-grade titanium dioxide, the titanium dioxide is uniformly coated on the surface of the matrix, the coating rate is high, the binding property is good, the surface activation energy of the composite material is high, the chemical activity, the oxidizing capability and the existence of hydroxyl are stronger, and the invention is suitable for being applied to the fields of papermaking, coating and the like as chemical filler, and the filling proportion is high and the filling effect is good.
And sodium pyrophosphate and diethyl phthalate are used as dispersing agents of hydrated calcium silicate, 6- (2, 3-dimethyl maleimide) hexyl methacrylate and 4- (N-maleimide methyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt are used as coating agents of the nano titanium dioxide, and the nano titanium dioxide coating agent replaces assistants such as sodium silicate, meta-titanic acid and the like in the prior art, has simple process implementation, good dispersing and coating effects, and the titanium dioxide and the matrix hydrated calcium silicate are tightly combined, and various raw materials are nontoxic and harmless in the production process, so that the nano titanium dioxide coating agent has a certain protection effect on environmental resources.
Finally, the nano-scale titanium dioxide and the hydrated calcium silicate are combined in a heating and high-speed stirring system, and finally the nano-scale titanium dioxide fine particles are attached on the surface structure of the hydrated calcium silicate, so that the combination strength of the hydrated calcium silicate and the titanium dioxide is far higher than that of the traditional composite modification.
Example 4
The embodiment discloses a preparation method of composite calcium carbonate-titanium dioxide, which comprises the following steps:
1) 25.00g of sodium pyrophosphate solution with the mass concentration of 16.0% and 120g of ethanol solution of diethyl phthalate with the mass concentration of 10.5% are mixed to prepare a dispersing agent for standby; wherein, the mol ratio of the sodium pyrophosphate to the diethyl phthalate is 1:3.8.
2) 30g of 6- (2, 3-dimethylmaleimide) hexyl methacrylate solution with the mass concentration of 5.0% and 355g of 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt solution with the mass concentration of 10% are mixed to prepare a coating agent for standby, wherein the molar ratio of 6- (2, 3-dimethylmaleimide) hexyl methacrylate to 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt is 1:2.6.
3) Taking 5kg of hydrated calcium silicate slurry with the mass concentration of 12%, adding 14.5g of the prepared dispersing agent, and carrying out ultrasonic vibration mixing to obtain calcium carbonate mixed solution.
4) 400g of titanium dioxide slurry with the mass concentration of 30% is taken, 2.5g of the prepared coating agent is added, and high-speed stirring is carried out to obtain titanium dioxide mixed solution.
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring rotation speed at 650r/min during the period, keeping the mixed solution from sedimentation, heating to 90 ℃ after complete mixing, quickly stirring at 1200r/min, carrying out solid-liquid separation on slurry after mixing for 85min, sequentially filtering and washing the mixture, spraying 2.8L of hot water at 75 ℃ in the washing process, drying and collecting after washing, and finally obtaining the hydrated calcium silicate-titanium dioxide composite product.
FIG. 2 is a scanning electron microscope image of the calcium carbonate-titanium dioxide composite material prepared in this example; the comparison of the properties of the samples in this example and example 3 is shown in Table 4.
Table 4 sample performance metrics for examples 3 and 4
| Sample numbering | Whiteness (%) | Hiding power (g/m) 2 ) | Oil absorption (g/100 g) | Brightness of light | Photocatalytic Activity |
| Example 3 | 98.3 | 22.9 | 58.6 | 95.6 | 0.23 |
| Example 4 | 98.9 | 23.8 | 62.4 | 96.3 | 0.32 |
Note that: the photocatalytic activity value characterizes the weatherability of the composite material, the lower the photocatalytic activity value, the better the weatherability.
As can be seen by data analysis and comparison, the sample of example 4 using calcium silicate hydrate as filler matrix has higher hiding power and oil absorption value, and the calcium silicate hydrate is used as carrier to load TiO 2 Better dispersibility and thus better hiding power. And the hydrated calcium silicate has higher oil absorption value than calcium carbonate itself, so that TiO is loaded 2 Still has a higher oil absorption value.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The preparation method of the composite calcium carbonate-titanium dioxide is characterized by comprising the following steps:
s10, adding a dispersing agent into calcium carbonate slurry, and fully mixing to obtain calcium carbonate mixed solution with uniformly dispersed calcium carbonate;
s20, adding a coating agent into the titanium dioxide slurry, and rapidly and fully stirring to uniformly coat the coating agent on the surfaces of the nano titanium dioxide particles to obtain uniformly dispersed titanium dioxide mixed solution;
s30, slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, and keeping stirring during the period to ensure that the mixed solution does not settle and is fully and uniformly mixed to obtain the calcium carbonate-titanium dioxide mixed solution;
s40, heating the calcium carbonate-titanium dioxide mixed solution, rapidly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; filtering, washing and drying the solid mixture to obtain a finished product of which the surface of the calcium carbonate powder is uniformly adhered with titanium dioxide fine particles, thus obtaining a calcium carbonate-titanium dioxide composite product;
in the step S10, the calcium carbonate slurry is light calcium carbonate slurry with the concentration of 6% -15%;
the dispersant in the step S10 is a mixed solution obtained by mixing 0.5% -2.5% of isobutanol solution and 0.9% -2.8% of 2-ethylhexanol solution; the molar ratio of the isobutanol to the 2-ethylhexanol in the mixed solution is 1:1-1:2;
the coating agent in the step S20 is a mixed solution obtained by mixing 0.2% -1.0% of a vinyl alcohol solution and 0.5% -1.2% of an acrylic acid solution, wherein the molar ratio of the vinyl alcohol to the acrylic acid in the mixed solution is 2:1-1:1.
2. The method for preparing composite calcium carbonate-titanium dioxide according to claim 1, wherein in step S10, the addition amount of the dispersant is 0.5% -1.5% of the weight of the dry weight of the light calcium silicate; in the step S20, the concentration of the titanium dioxide slurry is 15% -20%.
3. The method for preparing composite calcium carbonate-titanium dioxide according to claim 2, wherein in step S20, the addition amount of the coating agent is 1.5% -2.0% of the weight of the dry basis of the nano titanium dioxide.
4. The method for preparing composite calcium carbonate-titanium dioxide according to claim 2, wherein in step S30, the mixing ratio of the titanium dioxide mixed solution and the calcium carbonate mixed solution satisfies the condition that the mass ratio of dry-based titanium dioxide to dry-based calcium carbonate is 0.1-0.15.
5. The preparation method of the composite calcium carbonate-titanium dioxide is characterized by comprising the following steps:
s10, adding a dispersing agent into calcium carbonate slurry, and fully mixing to obtain calcium carbonate mixed solution with uniformly dispersed calcium carbonate;
s20, adding a coating agent into the titanium dioxide slurry, and rapidly and fully stirring to uniformly coat the coating agent on the surfaces of the nano titanium dioxide particles to obtain uniformly dispersed titanium dioxide mixed solution;
s30, slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, and keeping stirring during the period to ensure that the mixed solution does not settle and is fully and uniformly mixed to obtain the calcium carbonate-titanium dioxide mixed solution;
s40, heating the calcium carbonate-titanium dioxide mixed solution, rapidly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; filtering, washing and drying the solid mixture to obtain a finished product of which the surface of the calcium carbonate powder is uniformly adhered with titanium dioxide fine particles, thus obtaining a calcium carbonate-titanium dioxide composite product;
in the step S10, the calcium carbonate slurry is 9% -15% calcium carbonate slurry; the addition amount of the dispersing agent is 2.0-3.5% of the dry weight of the hydrated calcium silicate;
the dispersant in the step S10 is a mixed solution of sodium pyrophosphate solution and diethyl phthalate ethanol solution; wherein, the mass concentration of the sodium pyrophosphate solution is 12.5-18.5%; the mass concentration of the ethanol solution of diethyl phthalate is 8.0% -11.5%; the molar ratio of the sodium pyrophosphate to the diethyl phthalate in the mixed solution is 1:3-1:5;
the coating agent in the step S20 is a mixed solution obtained by mixing a 6- (2, 3-dimethylmaleimide) hexyl methacrylate solution with the mass concentration of 2.5% -5.0% and a 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt solution with the mass concentration of 5.5% -10%, wherein the molar ratio of the 6- (2, 3-dimethylmaleimide) hexyl methacrylate to the 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfosuccinimidyl ester sodium salt in the mixed solution is 1:2-1:4.
6. The method for preparing composite calcium carbonate-titanium pigment according to claim 5, wherein in step S20, the concentration of the titanium pigment slurry is 21% -35%; the addition amount of the coating agent is 2.1-3.0% of the weight of the dry basis of the nano titanium dioxide.
7. The method for preparing composite calcium carbonate-titanium dioxide according to claim 5, wherein in step S30, the mixing ratio of the titanium dioxide mixed solution and the calcium carbonate mixed solution satisfies the condition that the mass ratio of dry-based titanium dioxide to dry-based calcium carbonate is 0.2-0.25.
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| US5886069A (en) * | 1995-11-13 | 1999-03-23 | E. I. Du Pont De Nemours And Company | Titanium dioxide particles having substantially discrete inorganic particles dispersed on their surfaces |
| CN100582170C (en) * | 2007-08-07 | 2010-01-20 | 王刚 | Composite titanium white powder |
| CN103194098B (en) * | 2013-04-07 | 2015-04-08 | 攀枝花学院 | Preparation method of composite titanium dioxide |
| CN104387807A (en) * | 2014-10-31 | 2015-03-04 | 天津市欣德泰铁粉有限公司 | Preparation method of composite titanium dioxide |
| WO2016137459A1 (en) * | 2015-02-25 | 2016-09-01 | The Chemours Company Tt, Llc | Core/shell particles comprising a titanium dioxide core |
| CN105754378B (en) * | 2016-03-23 | 2018-11-09 | 河南鑫泰钙业有限公司 | A kind of calcium base titanium dioxide and its preparation process |
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| CN107353673A (en) * | 2017-06-12 | 2017-11-17 | 江苏特丰新材料科技有限公司 | Titanium dioxide that surface is modified and preparation method thereof |
| CN108440997A (en) * | 2018-04-26 | 2018-08-24 | 上杭汉晶新材料科技有限公司 | A kind of composite titanium dioxide and preparation method thereof |
| CN114716846A (en) * | 2021-01-04 | 2022-07-08 | 北京橡胶工业研究设计院有限公司 | Method for preparing composite titanium dioxide by using titanium dioxide coated calcium carbonate |
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| CN105778569A (en) * | 2016-05-05 | 2016-07-20 | 中钛集团洛阳市裕星化工有限公司 | Method for preparing composite titanium dioxide powder with titanium-coated light calcium carbonate |
| CN107936619A (en) * | 2017-11-28 | 2018-04-20 | 广西雅照钛白有限公司 | A kind of composite titanium dioxide and its manufacture method |
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