CN115197603A - Preparation method of composite calcium carbonate-titanium dioxide - Google Patents

Preparation method of composite calcium carbonate-titanium dioxide Download PDF

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CN115197603A
CN115197603A CN202210807398.4A CN202210807398A CN115197603A CN 115197603 A CN115197603 A CN 115197603A CN 202210807398 A CN202210807398 A CN 202210807398A CN 115197603 A CN115197603 A CN 115197603A
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titanium dioxide
calcium carbonate
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CN115197603B (en
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徐鹏
齐建军
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Inner Mongolia Punuosi New Material Technology Co ltd
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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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
    • 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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    • D21H17/63—Inorganic compounds
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    • D21H17/675—Oxides, hydroxides or carbonates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention provides a preparation method of composite calcium carbonate-titanium dioxide, which comprises the following steps: adding a dispersant into the calcium carbonate slurry, and fully mixing; adding the coating agent into the titanium dioxide slurry, and quickly and fully stirring to ensure that the coating agent is uniformly coated on the surface 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, quickly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; and filtering, washing and drying the solid mixture to obtain a finished product with the calcium carbonate powder surface uniformly attached with the titanium dioxide fine particles, namely obtaining the calcium carbonate-titanium dioxide composite product. The composite material has high surface activation energy, strong chemical activity, strong oxidation capacity and strong existence of hydroxyl, is suitable to be used as chemical filler in the fields of papermaking, coating and the like, and has high filling proportion and good filling effect.

Description

Preparation method of composite calcium carbonate-titanium dioxide
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
Nano titanium dioxide (TiO) 2 ) As a photocatalyst, the N-type semiconductor material with excellent performance can fully utilize solar energy,the nano-functional material is efficient, energy-saving and environment-friendly, shows better light stability and higher reaction activity when in reaction, is non-toxic and free of secondary pollution, and is the nano-functional material with the widest application prospect at present. Is widely applied to the fields of wastewater treatment, air purification, sterilization, medical technology, environment-friendly material preparation and the like.
Calcium carbonate is 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 coatings, plastics, papermaking, rubber, printing ink and the like. In particular, calcium carbonate is receiving more and more attention in the coating field, and in the water-based coating industry, the calcium carbonate can prevent the coating from settling, so that the coating has good dispersibility and high glossiness, and the dosage of the calcium carbonate in the water-based coating accounts for 20-60%. The calcium carbonate in the coating not only plays a role of a skeleton, but also can increase the thickness of a coating, improve the wear resistance of the coating and obviously improve the adhesive force of the coating. The calcium carbonate is added into the coating, so that the rheological property of the coating, the toughness of the coating, the water resistance, the weather resistance and the stability can be changed.
However, the existing calcium carbonate has the defects of weak covering power, easy chalking phenomenon under long-time sunlight irradiation and the like, which limits the application range of the calcium carbonate. In addition, calcium carbonate has a low whiteness and cannot be used as a pigment aid in paints.
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 step-by-step completion of the coating of the calcium carbonate and the coating of the titanium dioxide in the carbonation reaction process, but the method has large added titanium dioxide amount, improves the production cost, has complex technical operation process and faces certain difficulty in realizing industrialization. Patent nos. CN1444543A and CN103897438A provide a process for preparing titanium dioxide-calcium carbonate composite particles, characterized in that titanium dioxide particles are directly coated on the surface of calcium carbonate by carbonization, which is carried out by introducing a mixture of carbon dioxide and air into calcium hydroxide slurry under stirring until the pH of the slurry is 7. The above patent firstly proposes a technology for preparing titanium dioxide-calcium carbonate composite particles by using a carbonization method, realizes partial coating of titanium dioxide on the surface of calcium carbonate, and improves the whiteness of the product. However, the titanium dioxide-calcium carbonate composite particles prepared by the method have the phenomena of unstable composite particles, easy peeling 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 metatitanic 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 raw material of the titanium dioxide is changed into metatitanic acid from commercial titanium dioxide, so that the production cost is reduced, the calcium carbonate is coated firstly and then with titanium dioxide in the preparation process, but the difference between the specific gravities of the titanium dioxide and the calcium carbonate is large, so that the coating rate of calcium carbonate in the product is large, the particle size of metatitanic acid is dozens of nanometers, agglomeration is easy, the combination of metatitanic acid particles subjected to secondary agglomeration and calcium carbonate is not firm enough, the required drying temperature is high, and the time is long. In addition, the process for preparing the metacarpic acid by the sulfuric acid method causes 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 technical problem 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 the calcium carbonate slurry, and fully mixing to obtain a calcium carbonate mixed solution with uniformly dispersed calcium carbonate;
s20, adding a coating agent into the titanium dioxide slurry, and quickly and fully stirring to ensure that the coating agent is uniformly coated on the surfaces of the nano titanium dioxide particles to obtain uniformly dispersed titanium dioxide mixed liquid;
s30, slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, and keeping stirring in the process to ensure that the mixed solution is not settled and is fully and uniformly mixed to obtain calcium carbonate-titanium dioxide mixed solution;
s40, heating the calcium carbonate-titanium dioxide mixed solution, quickly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; and filtering, washing and drying the solid mixture to obtain a finished product with the calcium carbonate powder surface uniformly attached with the titanium dioxide fine particles, namely obtaining the calcium carbonate-titanium dioxide composite product.
Further, in step S10, the calcium carbonate slurry is light calcium carbonate slurry with the concentration of 6-15%; in 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 step S20, the amount of the coating agent added is 1.5% -2.0% of the dry weight of the nano titanium dioxide.
Further, in the step S10, the dispersant is a mixed solution obtained by mixing 0.5% -2.5% isobutanol solution and 0.9% -2.8% 2-ethylhexanol solution by mass concentration; the molar ratio of isobutanol to 2-ethylhexanol in the mixture is 1 to 1.
Further, in step S20, the coating agent is a mixed solution obtained by mixing 0.2% to 1.0% by mass of a vinyl alcohol solution and 0.5% to 1.2% by mass of an acrylic acid solution, and the molar ratio of vinyl alcohol to acrylic acid in the mixed solution is from 2 to 1.
Further, in step S30, the mixing ratio of the titanium dioxide mixed solution and the calcium carbonate mixed solution meets 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 step S40, the heating temperature is 65-85 ℃, the stirring speed is 350-600 r/min, and the mixing time is 15-40 min.
Further, after the reaction in step S40 is completed, (without cooling) solid-liquid separation and washing are immediately performed, the solid after solid-liquid separation is collected, and spray washing is performed using 1.5 to 2 times the volume of hot water at a temperature of 45 ℃ to 55 ℃.
Preferably, in step S10, ultrasonic agitation is used for mixing.
When the light calcium carbonate is used as a matrix, the light calcium carbonate has the crystal form of calcite and the microscopic form of spindle, and has the characteristics of high whiteness, strong covering power, high weather resistance and the like.
In addition, the invention uses isobutanol and 2-ethylhexanol as the dispersing agent of the light calcium carbonate, uses vinyl alcohol and acrylic acid as the coating agent of the nano titanium dioxide, replaces the prior art to make water glass, metatitanic acid and other auxiliary agents, has simple process realization, good dispersing and coating effects, close combination of the titanium dioxide and the matrix light calcium carbonate, and no toxicity and harm of various raw materials in the production process, thereby playing a certain role in protecting environmental resources.
Finally, the nano titanium dioxide and the light calcium carbonate are combined in a heating and high-speed stirring system, and finally, fine particles of the nano titanium dioxide are attached to the surface structure of the light calcium carbonate, and the bonding 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 a calcium silicate hydrate slurry with a concentration of 9% to 15%;
in step S10, the dispersant is added in an amount of 2.0 to 3.5 percent by weight based on the dry weight of the calcium silicate hydrate.
Further, in 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 dry weight 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 diethyl phthalate ethanol solution is 8.0% -11.5%; the molar ratio of the sodium pyrophosphate to the diethyl phthalate in the mixed solution is (1).
Further, in step S20, the coating agent is a mixed solution obtained by mixing a solution of 6- (2, 3-dimethylmaleimide) hexyl methacrylate with a mass concentration of 2.5% to 5.0% and a solution of sodium sulfosuccinimidyl 4- (N-maleimidomethyl) cyclohexane-1-carboxylate with a mass concentration of 5.5% to 10%, wherein the molar ratio of 6- (2, 3-dimethylmaleimide) hexyl methacrylate to sodium sulfosuccinimidyl 4- (N-maleimidomethyl) cyclohexane-1-carboxylate in the mixed solution is 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 0.2-0.25.
Further, in step S40, the heating temperature is 88-95 ℃, the stirring speed is 650-1200 r/min, and the mixing time is 50-90 min.
Further, after the reaction is sufficiently performed in step S40, solid-liquid separation and washing are immediately performed (without cooling), the solid after solid-liquid separation is collected, and spray washing is performed using hot water of which the volume is 3.5 to 4 times that of the solid, and the temperature of the hot water is 60 ℃ to 75 ℃.
When the calcium silicate hydrate is used as a matrix, the crystal form of the calcium silicate hydrate is amorphous, the microscopic form of the calcium silicate hydrate is a cellular porous structure, and the calcium silicate hydrate has the characteristics of higher whiteness, stronger covering power, strong weather resistance and the like.
In the invention, 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 sulfo succinimide ester sodium salt are used as coating agents of nano titanium dioxide instead of assistants such as water glass and metatitanic acid in the prior art, the process is simple to realize, the dispersing and coating effects are good, 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 a certain protection effect on environmental resources is achieved.
Finally, the nano titanium dioxide and the hydrated calcium silicate are combined in a heating and high-speed stirring system, and finally, fine particles of the nano titanium dioxide are attached to the surface structure of the hydrated calcium silicate, so that the bonding 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 present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description in the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
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 dioxide composite material prepared in embodiment 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The present invention will be further explained with reference to specific embodiments.
Example 1
The preparation method of the composite calcium carbonate-titanium dioxide disclosed by the embodiment comprises the following steps:
1) Mixing 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% to prepare a dispersing agent for later use, wherein the molar ratio of the isobutanol to the 2-ethylhexanol is 1;
2) Mixing 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% to prepare a coating agent for later use, wherein the molar ratio of the vinyl alcohol to the acrylic acid is 1;
3) 5kg of light calcium carbonate slurry with the mass concentration of 10% is taken, 5g of the prepared dispersing agent is added, and then ultrasonic oscillation mixing is carried out 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 high speed to prepare titanium dioxide mixed solution;
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring speed of 350r/min in the period of no sedimentation of the mixed solution, heating to 75 ℃ after complete mixing, carrying out rapid stirring at the speed of 550r/min, carrying out solid-liquid separation on the slurry after mixing for 30min, and then sequentially filtering and washing the mixture; wherein 1.1L of hot water with the temperature of 50 ℃ is used for spraying in the washing process, and after washing, the calcium carbonate-titanium dioxide composite product is finally obtained by drying and collecting.
Referring to table 1, when ash content of the obtained pulp is tested after being made into paper, ash content of the pulp in this example can reach 29.48%, and filler retention rate can reach 75.26%, which is much higher than paper ash and filler retention rate of GCC filler and PCC filler which are directly used as paper making filler and added into paper.
In addition, the strength of the paper under the condition of the embodiment is higher than that of the paper made by selecting the traditional GCC and PCC as fillers.
Table 1 comparison of the properties of the process with GCC and PCC filler sheets under the conditions of example 1
Figure BDA0003738700670000081
The embodiment solves the technical problems that the nano-scale titanium dioxide is easy to agglomerate, the production process is complex, the calcium carbonate coating rate is low and the like in the prior art. Under the condition of specific dispersing agent and coating agent, the surfaces of titanium white particles are coated with adhesive in advance, then the titanium white particles are mixed with light calcium carbonate slurry, and the titanium white is uniformly coated on the surface of calcium carbonate by heating and high-speed stirring. The patent firstly provides a technology for compounding titanium dioxide and calcium carbonate by synergistically utilizing a dispersing agent and a coating agent, so that the titanium dioxide is uniformly coated on the surface of the calcium carbonate, the structural stability of the composite material is improved, the composite material adopts a simple and easy-to-realize process method, the production process is green, environment-friendly, low-carbon and energy-saving, the product dispersibility and weather resistance are improved, the whiteness, the dry-wet covering capability and the color reducing capability of the material are improved, and the composite material is successfully applied to 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) Mixing 15.00g of isobutanol solution with the mass concentration of 1.5% with 22.73g of 2-ethylhexanol solution with the mass concentration of 2.0% to prepare a dispersing agent for later use, wherein the molar ratio of isobutanol to 2-ethylhexanol is 1.5;
2) Mixing 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% to prepare a coating agent for later use, wherein the molar ratio of the vinyl alcohol to the acrylic acid is 1.5;
3) Taking 10kg of light calcium carbonate slurry with the mass concentration of 10%, adding 12g of the prepared dispersing agent, and then carrying out ultrasonic oscillation mixing to obtain a calcium carbonate mixed solution;
4) Taking 200g of titanium dioxide slurry with the mass concentration of 18%, adding 0.65g of the prepared coating agent, and stirring at high speed to obtain titanium dioxide mixed solution;
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring speed at 380r/min in the period of time to prevent the mixed solution from settling, heating to 80 ℃ after the mixed solution is completely mixed, quickly stirring at 600r/min, mixing for 25min, carrying out solid-liquid separation on the slurry, sequentially filtering and washing the mixture, wherein 1.9L of hot water with the temperature of 55 ℃ is used for spraying in the washing process, and drying and collecting after washing to finally obtain the calcium carbonate-titanium dioxide composite product.
FIG. 1 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 of this example with those of example 1 is shown in Table 2.
Table 2 examples 1, 2 sample performance indices
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: the photocatalytic activity value characterizes the weatherability of the composite material, the lower the photocatalytic activity value, the better the weatherability.
Example 3
The preparation method of the composite calcium carbonate-titanium dioxide disclosed by the embodiment comprises the following steps:
1) Mixing 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% to prepare a dispersing agent for later use; wherein the molar ratio of the sodium pyrophosphate to the diethyl phthalate is 1.
2) 20g of 6- (2, 3-dimethylmaleimide) hexyl methacrylate solution with the mass concentration of 3 percent and 315g of 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfo-succinimide ester sodium salt solution with the mass concentration of 8.5 percent are mixed to prepare the coating agent for standby, wherein the molar ratio of the 6- (2, 3-dimethylmaleimide) hexyl methacrylate to the 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfo-succinimide ester sodium salt is 1.
3) 5kg of calcium silicate hydrate slurry with the mass concentration of 10% is taken, and is added with 12.5g of the prepared dispersant for ultrasonic oscillation mixing to obtain calcium carbonate mixed liquor.
4) And taking 400g of titanium dioxide slurry with the mass concentration of 25%, adding 2.5g of the prepared coating agent, and stirring at high speed to obtain titanium dioxide mixed solution.
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring speed of 650r/min in the period of no sedimentation of the mixed solution, heating to 90 ℃ after complete mixing, carrying out rapid stirring at the speed of 1100r/min, carrying out solid-liquid separation on the slurry after mixing for 60min, sequentially filtering and washing the mixture, wherein 2.4L of hot water with the temperature of 65 ℃ is used for spraying in the washing process, and drying and collecting after washing to finally obtain the calcium silicate hydrate-titanium dioxide composite product.
Referring to table 3, after the obtained pulp is made into paper, ash content is tested, ash content can reach 36.84%, and filler retention rate can reach 82.37%, which is far higher than paper ash and filler retention rate of GCC filler and PCC filler which are directly used as paper making filler and added into paper; in addition, the strength of the paper under the conditions of the embodiment is higher than that of the paper made by selecting the traditional GCC and PCC as fillers.
Table 3 comparison of the properties of the paper with GCC and PCC filler according to the method under the conditions of example 1
Figure BDA0003738700670000101
Figure BDA0003738700670000111
The invention uses calcium silicate hydrate as a substrate, the crystal form of the calcium silicate hydrate is amorphous, the microscopic form is a cellular porous structure, the calcium silicate hydrate has the characteristics of higher whiteness, stronger covering power, strong weather resistance and the like, the nano-titanium dioxide is compounded on the surface of the substrate, the titanium dioxide is uniformly coated on the surface of the substrate, the coating rate is high, the associativity is good, the surface activation energy of the composite material is high, the composite material has stronger chemical activity, oxidation capacity and hydroxyl existence, and the calcium silicate hydrate is suitable for being used as a chemical filler in the fields of papermaking, coating and the like, and has high filling proportion and good filling effect.
In the invention, 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 sulfonic succinimide ester sodium salt are used as coating agents of nano titanium dioxide instead of the prior art, such as water glass, metatitanic acid and other auxiliary agents are adopted, the process is simple to realize, the dispersing and coating effects are good, the titanium dioxide is tightly combined with the matrix hydrated calcium silicate, and various raw materials are non-toxic and harmless in the production process, so that a certain protection effect is provided for environmental resources.
Finally, the nano titanium dioxide and the hydrated calcium silicate are combined in a heating and high-speed stirring system, and finally, fine particles of the nano titanium dioxide are attached to the surface structure of the hydrated calcium silicate, so that the bonding 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) Mixing 25.00g of sodium pyrophosphate solution with mass concentration of 16.0% and 120g of diethyl phthalate ethanol solution with mass concentration of 10.5% to prepare a dispersing agent for later use; wherein the molar ratio of the sodium pyrophosphate to the diethyl phthalate is 1.
2) A coating agent is prepared by mixing 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 sulfo succinimide ester sodium salt solution with the mass concentration of 10% to prepare a coating agent for later use, wherein the molar ratio of the 6- (2, 3-dimethylmaleimide) hexyl methacrylate to the 4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid sulfo succinimide ester sodium salt is 1.
3) 5kg of calcium silicate hydrate slurry with the mass concentration of 12% is taken, 14.5g of the prepared dispersing agent is added, and then ultrasonic oscillation mixing is carried out to obtain calcium carbonate mixed liquor.
4) Taking 400g of titanium dioxide slurry with the mass concentration of 30%, adding 2.5g of the prepared coating agent, and stirring at high speed to obtain a titanium dioxide mixed solution.
5) Slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, keeping the stirring speed of 650r/min in the period of no sedimentation of the mixed solution, heating to 90 ℃ after complete mixing, carrying out rapid stirring at the speed of 1200r/min, carrying out solid-liquid separation on the slurry after mixing for 85min, sequentially filtering and washing the mixture, wherein 2.8L of hot water with the temperature of 75 ℃ is used for spraying in the washing process, and drying and collecting after washing to finally obtain the calcium silicate hydrate-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 of this example with those of example 3 is shown in Table 4.
Table 4 example 3 and 4 sample performance indices
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: the photocatalytic activity value characterizes the weatherability of the composite material, the lower the photocatalytic activity value, the better the weatherability.
By comparing the data analysis, the calcium silicate hydrate is usedExample 4, which is a filler matrix, has higher hiding power and oil absorption value, and calcium silicate hydrate is used as a carrier to load TiO 2 The time dispersion is better and therefore the hiding power is better. And the hydrated calcium silicate has higher oil absorption value compared with calcium carbonate, so that the TiO is loaded 2 Still has a higher oil absorption value.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The preparation method of the composite calcium carbonate-titanium dioxide is characterized by comprising the following steps:
s10, adding a dispersing agent into the calcium carbonate slurry, and fully mixing to obtain a calcium carbonate mixed solution with uniformly dispersed calcium carbonate;
s20, adding the coating agent into the titanium dioxide slurry, and quickly and fully stirring to ensure that the coating agent is uniformly coated on the surfaces of the nano titanium dioxide particles to obtain uniformly dispersed titanium dioxide mixed liquor;
s30, slowly pouring the titanium dioxide mixed solution into the calcium carbonate mixed solution, and keeping stirring in the process to ensure that the mixed solution is not settled and is fully and uniformly mixed to obtain calcium carbonate-titanium dioxide mixed solution;
s40, heating the calcium carbonate-titanium dioxide mixed solution, quickly stirring, and carrying out solid-liquid separation after full reaction to obtain a solid mixture; and filtering, washing and drying the solid mixture to obtain a finished product with the calcium carbonate powder surface uniformly attached with the titanium dioxide fine particles, namely obtaining the calcium carbonate-titanium dioxide composite product.
2. The method for preparing composite calcium carbonate-titanium dioxide according to claim 1, wherein in step S10, the calcium carbonate slurry is light calcium carbonate slurry with a 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; in 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 amount of the coating agent added is 1.5-2.0% of the dry weight of the nano titanium dioxide.
4. The preparation method of the composite calcium carbonate-titanium dioxide according to claim 2, wherein the dispersant in the step S10 is a mixed solution obtained by mixing 0.5-2.5% by mass of isobutanol solution and 0.9-2.8% by mass of 2-ethylhexanol solution; the molar ratio of isobutanol to 2-ethylhexanol in the mixture is 1 to 1.
5. The preparation method of the composite calcium carbonate-titanium dioxide according to claim 2, wherein in step S20, the coating agent is a mixed solution obtained by mixing 0.2-1.0% by mass of a vinyl alcohol solution and 0.5-1.2% by mass of an acrylic acid solution, and the molar ratio of the vinyl alcohol to the acrylic acid in the mixed solution is 2.
6. 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 to the calcium carbonate mixed solution satisfies the condition that the mass ratio of the dry titanium dioxide to the dry calcium carbonate is 0.1-0.15.
7. The method for preparing composite calcium carbonate-titanium dioxide according to claim 1, wherein in 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.
8. The method for preparing composite calcium carbonate-titanium dioxide according to claim 7, wherein in 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 dry weight of the nano titanium dioxide.
9. The method for preparing composite calcium carbonate-titanium dioxide according to claim 7, wherein the dispersant in step S10 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 diethyl phthalate ethanol solution is 8.0-11.5%; the molar ratio of the sodium pyrophosphate to the diethyl phthalate in the mixed solution is (1).
10. The preparation method of composite calcium carbonate-titanium dioxide according to claim 7, wherein in step S20, the coating agent is a mixed solution obtained by mixing a solution of 6- (2, 3-dimethylmaleimide) hexyl methacrylate with a mass concentration of 2.5% to 5.0% and a solution of sodium sulfosuccinimidyl 4- (N-maleimidomethyl) cyclohexane-1-carboxylate with a mass concentration of 5.5% to 10%, and the molar ratio of 6- (2, 3-dimethylmaleimide) hexyl methacrylate to sodium sulfosuccinimidyl 4- (N-maleimidomethyl) cyclohexane-1-carboxylate in the mixed solution is 1;
in step S30, the mixing ratio of the titanium dioxide mixed solution and the calcium carbonate mixed solution meets the condition that the mass ratio of the dry-based titanium dioxide to the dry-based calcium carbonate is 0.2-0.25.
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