CN111533167A - Preparation method of modified titanium dioxide, modified titanium dioxide and application - Google Patents
Preparation method of modified titanium dioxide, modified titanium dioxide and application Download PDFInfo
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- CN111533167A CN111533167A CN202010399083.1A CN202010399083A CN111533167A CN 111533167 A CN111533167 A CN 111533167A CN 202010399083 A CN202010399083 A CN 202010399083A CN 111533167 A CN111533167 A CN 111533167A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention provides a preparation method of modified titanium dioxide, the modified titanium dioxide and application, and solves the technical problems that the color mortar in the prior art is poor in weather resistance and is easy to generate saltpetering for dry-mixed mortar using portland cement as a cementing material. The preparation method comprises the following steps: (1) gasifying the butyl titanate; (2) adding water into a reactor for reaction to obtain nano TiO2(ii) a (3) Cooling to 20-25 ℃; (4) and (5) screening to obtain a finished product of the modified titanium dioxide. The modified titanium dioxide prepared by the method can be used as a weather-resistant additive to be added into the color dry-mixed mortar, and the modified nano titanium dioxide absorbs ultraviolet light and reflects a large amount of visible light, so that the color vividness can be enhanced; simultaneously ensuring that polymers in the cement paste and the cement paste are not subjected to linear expansion coefficientAnd the difference is separated from each other, thereby ensuring the adhesion of the polymer to the portland cement, and the refinement and filling of capillary pores.
Description
Technical Field
The invention relates to titanium dioxide, and in particular relates to a preparation method of modified titanium dioxide, the modified titanium dioxide and application.
Background
The color mortar is one kind of special mortar for decorating inner and outer walls of building and can resist the damage of high temperature, low temperature and humidity and beautify the decorated building. It is widely used in industry and civil construction because of its bright and durable color.
With the increase of the pollution degree of the external environment and the change of the climate, the weather resistance of the color mortar is gradually reduced. The weather resistance is the tolerance capability of materials such as paint, building plastic, rubber products and the like to withstand the outdoor weather, such as comprehensive damage caused by illumination, cold and heat, wind and rain, bacteria and the like. The most obvious performance is that the color mortar is hydrated by ordinary portland cement with Ca (OH) under the action of rainwater2With the water leaching out, saltpetering occurs. The efflorescence phenomenon is commonly called whitening or blooming, and is a phenomenon frequently occurring on the surface of a building, and includes a mortar surface, a concrete surface, a clay brick surface, a tile surface and the like. The efflorescence is generally in the form of white powder, flocs or flakes. This occurs on many building walls, particularly where the rain fly and wall join, at roof drains, and on many plastered mortar surfaces. It is just like skin disease to human body to the building, is harmful to the outward appearance pleasing to the eye, seriously influences the building engineering impression quality, sometimes still can influence its colouring effect and basic unit and surface finishing, wainscot, whitewash the bonding quality of the layer, still can cause the cracking hollowing of the plastering mortar layer of the colored mortar. Therefore, during the construction of the color mortar, a layer of primer needs to be coated on the bottom layer in advance, and a side finish is made after the primer is finished, so that the purpose of preventing the color mortar from being efflorescent in a complex environment later is achieved.
In foreign countries, the phenomena of Efflorescence such as masonry walls have been described in large numbers in the early 19 th century, and Ritchie published the article Efflorescence in 1960. In the future, researchers have conducted a great deal of research on the problem of the ubiquitination, and have many research results on the formation mechanism and the prevention approach of the ubiquitination. Through a large amount of research of domestic and foreign scientists, the whiskering of cement systems is due to cementSoluble components in materials such as sand, stone and admixture are dissolved in water, and then precipitated on the surface of a hardened body or CO in the air is dissolved together with the evaporation of water on the surface of mortar2And the like to produce a white deposit. The chemical composition of these white substances varies depending on the materials used, the construction process, the time of occurrence, the season, the environment, and the like. According to the X-ray diffraction analysis result, Ca (OH) is common2、CaCO3、CaSO4、Na2SO4、Na2CO3、K2CO3And the like. For dry-mixed mortars using portland cement as cementitious material, the result is Ca (OH)2Is itself a hydration product, and is almost unavoidable for efflorescence.
The applicant has found that the prior art has at least the following technical problems:
the color mortar in the prior art has poor weather resistance, and is easy to cause efflorescence for dry-mixed mortar using portland cement as a cementing material.
Disclosure of Invention
The invention aims to provide a preparation method of modified titanium dioxide and the modified titanium dioxide, and aims to solve the technical problems that the color mortar in the prior art is poor in weather resistance and is easy to generate saltpetering for dry-mixed mortar using portland cement as a cementing material. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of modified titanium dioxide, which comprises the following steps:
a1, adding butyl titanate into a reactor, and gasifying the butyl titanate at the temperature of 40-130 ℃ under the protection of inert gas;
a2, adding water into a reactor, and reacting at 500-550 ℃ and 0.5 × 105Pa-1.5×105Pa, inert gas protection to obtain nano TiO2；
A3, obtaining the product of the step A2To nano TiO2Placing the mixture in an inert gas atmosphere to reduce the temperature to 20-25 ℃;
a4, cooling the TiO obtained in the step A32And (4) carrying out screen analysis to obtain a finished product of the modified titanium dioxide.
Further, in the step (4), the sieve analysis is to cool down the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100.
Further, in the step a2, the mass ratio of water to butyl titanate is 2: 1-20:1.
Further, in the step A2, the flow rate of the inert gas is 0.5L/min-1.2L/min, the flow rate of the water vapor is 1L/min-2L/min, and the reaction time is 20min-35 min.
Further, in the step A2, the flow rate of the inert gas is 1L/min, the flow rate of the water vapor is 1L/min, and the reaction time is 30 min.
Further, in the step A1 and the step A2, the inert gas is N2。
Further, in the step A3, the inert gas is CO2。
Further, in the step A2, the pressure is 0.5 × 105Pa-2×105Pa。
The invention provides modified titanium dioxide prepared by the preparation method.
The modified titanium dioxide prepared by the preparation method provided by the invention is applied to preparing color dry-mixed mortar.
The preparation method for preparing the color dry-mixed mortar by using the modified titanium dioxide prepared by the invention comprises the following steps:
(1) preparation of modified titanium white powder
A1, adding butyl titanate into a reactor, and gasifying the butyl titanate at the temperature of 40-130 ℃ under the protection of inert gas;
a2, adding water into a reactor, reacting at 500-550 ℃ and 0.5 × 105Pa～1.5×105Pa, inert gas protection to obtain nano TiO2(ii) a The mass ratio of the water to the butyl titanate is 2: 1-20:1
A3, and the nanometer TiO obtained in the step A22Placing the mixture in an inert gas atmosphere to reduce the temperature to 20-25 ℃;
a4, cooling the TiO obtained in the step A32Carrying out screen analysis, wherein the screen analysis is to cool the TiO obtained in the step (1) A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98%, the screen residue is less than 0.01%, the volatile matter at 105 ℃ is less than 0.05%, and the L value ranges from 98.5 to 100; obtaining a finished product of the modified titanium dioxide;
the chemical reaction process can be expressed by the following chemical reaction equation:
Ti(OC4H9)4+2H2O→TiO2+4C4H9OH
(2) preparation of modified mixture T-C
B1, adding chitosan and NaOH solution into a reaction container, and alkalizing the chitosan in the NaOH solution;
b2, adding isopropanol and ClCH into the reaction vessel in sequence2COOH is evenly stirred and then is placed for 2 to 3 hours at the temperature of between 15 and 25 ℃; then heating to 65-70 ℃, and preserving the heat for 1.5-2 h; then adjusting the pH value to 6-8;
b3, adding the modified titanium dioxide prepared in the step (1) into a reaction container, uniformly stirring to obtain a mixture, filtering the mixture, and keeping a precipitate;
b4, using CH in turn for the precipitate obtained in the step B33CH2Washing with OH solution and anhydrous methanol to ensure the activation of chitosan and maintain the activity of titanium pigment;
b5, drying at 50-70 ℃ after washing to obtain a modified mixture T-C;
(3) preparation of N, O carboxymethyl chitosan
C1, dissolving the modified mixture T-C prepared in the step (2) in water at the temperature of 30-40 ℃ to obtain a solution a;
C2、adding CH to the solution a obtained in step C13OCH3Carrying out precipitation reaction on the solution, filtering after the reaction is finished, and keeping the precipitate;
c3 precipitation obtained in step C2 with anhydrous CH3CH2OH washing, and then vacuum drying to obtain N, O carboxymethyl chitosan powder;
(4) preparation of mixture W
Uniformly mixing white portland cement, the modified mixture T-C obtained in the step (2) and the N, O carboxymethyl chitosan obtained in the step (3) according to a ratio to obtain a mixture W;
(5) preparation of finished product of colored dry-mixed mortar
And uniformly mixing the machine-made sand, the mixture W, the stone powder, the pigment, the redispersible latex powder, the hydroxypropyl methyl cellulose ether and the zeolite powder according to the proportion to obtain a finished product of the color dry-mixed mortar.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
according to the preparation method of the modified titanium dioxide and the modified titanium dioxide, the prepared modified titanium dioxide can be used as a weather-resistant additive to be added into color dry-mixed mortar, the modified titanium dioxide is in an anatase structure, the anatase structure can reflect a large amount of visible light of 400-700 nm, and can absorb the ultraviolet light of 300-400 nm more than rutile titanium dioxide, the temperature rising capability of the visible light is strong, so that the internal temperature of the mortar is increased, the cement paste and the polymer are separated from each other due to the fact that the thermal expansion coefficients of the cement paste and the polymer are different, and meanwhile, the polymer film is aged and cannot be compounded with the cement paste due to the fact that cross-linked molecules fall off when the polymer is irradiated by the ultraviolet light, so that the; the added modified nano titanium dioxide can reflect a large amount of visible light by absorbing ultraviolet light through the modified nano titanium dioxide, so that the color vividness is enhanced; the added modified titanium dioxide can ensure that a polymer in the cement paste and the cement paste can not be separated from each other due to the difference of linear expansion coefficients, so that the adhesion of the polymer to the portland cement, the thinning and the filling of capillary pores are ensured; under the condition of low temperature, the polymer film has small elastic modulus and large linear shrinkage, the polymer film can better play a role in bonding, the film can be better ensured to be tightly adhered to the surface of cement paste, the film and the cement paste are stably integrated, the good weather resistance of the color dry-mixed mortar can be ensured, and the efflorescence phenomenon can be reduced as much as possible.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
First, preparation example:
example 1:
preparing modified titanium dioxide:
raw materials (in parts by weight): 1 part of butyl titanate and 10 parts of water;
a1, adding butyl titanate into a reactor at 85 ℃ and N2Under protection, butyl titanate is gasified;
a2, adding water into a reactor, reacting at 525 ℃ and 1.01 × 105Pa、N2Under the protection of (1L/min of nitrogen flow, 1L/min of water vapor flow and 30min of reaction time), obtaining R818 type nano TiO2；
A3, and the nanometer TiO obtained in the step A22Placing in inert gas CO2Cooling to 23 ℃ in the atmosphere;
a4, cooling the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100, thus obtaining the finished product of the modified titanium dioxide.
Example 2:
preparing modified titanium dioxide:
raw materials (in parts by weight): 1 part of butyl titanate and 15 parts of water;
a1, adding butyl titanate into a reactorAt a temperature of 60 ℃ and N2Under protection, butyl titanate is gasified;
a2, adding water into the reactor, reacting at 510 deg.C and 1.5 × 105Pa、N2Under the protection of (1L/min of nitrogen flow, 1L/min of water vapor flow and 30min of reaction time), obtaining R818 type nano TiO2；
A3, and the nanometer TiO obtained in the step A22Placing in inert gas CO2Cooling to 22 ℃ in the atmosphere;
a4, cooling the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100, thus obtaining the finished product of the modified titanium dioxide.
Example 3:
preparing modified titanium dioxide:
raw materials (in parts by weight): 1 part of butyl titanate and 6 parts of water;
a1, adding butyl titanate into a reactor, and heating at 110 ℃ and N2Under protection, butyl titanate is gasified;
a2, adding water into the reactor, reacting at 530 ℃ and 0.5 × 105Pa、N2Under the protection of (1L/min of nitrogen flow, 1L/min of water vapor flow and 20min of reaction time), obtaining R818 type nano TiO2；
A3, and the nanometer TiO obtained in the step A22Placing in inert gas CO2Cooling to 24 ℃ in the atmosphere;
a4, cooling the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100, thus obtaining the finished product of the modified titanium dioxide.
Example 4:
preparing modified titanium dioxide:
raw materials (in parts by weight): 1 part of butyl titanate and 20 parts of water;
a1, adding butyl titanate into a reactor, and heating at 130 ℃ and N2Under protection, butyl titanate is gasified;
a2, adding water into the reactor, reacting at 550 ℃ and 1.2 × 105Pa、N2Under the protection of (1.2L/min nitrogen flow, 1.2L/min water vapor flow, 35min reaction time), to obtain R818 type nanometer TiO2；
A3, and the nanometer TiO obtained in the step A22Placing in inert gas CO2Cooling to 25 ℃ in the atmosphere;
a4, cooling the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100, thus obtaining the finished product of the modified titanium dioxide.
Example 5:
preparing modified titanium dioxide:
raw materials (in parts by weight): 1 part of butyl titanate and 2 parts of water;
a1, adding butyl titanate into a reactor at 40 ℃ and N2Under protection, butyl titanate is gasified;
a2, adding water into the reactor, reacting at 500 deg.C and 0.8 × 105Pa、N2Under the protection of (nitrogen flow is 0.5L/min, water vapor flow is 2.0L/min, reaction time is 20min) to obtain R818 type nano TiO2；
A3, and the nanometer TiO obtained in the step A22Placing in inert gas CO2Cooling to 20 ℃ in the atmosphere;
a4, cooling the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100, thus obtaining the finished product of the modified titanium dioxide.
Second, Experimental example
1. The modified titanium dioxide prepared in example 1 to example 5; the results of the physical and chemical property tests are shown in the following table 1:
TABLE 1 physicochemical Properties of modified titanium dioxide in examples 1-5
2. Preparation of a color Dry-Mixed mortar Using the modified titanium white prepared in examples 1 to 5 the following description of the raw materials in examples 1 to 5 apply:
white portland cement: the WPC strength grade is 42.5R, and the CaO content is 58% -65%: the whiteness is more than 80 percent;
and (3) machining sand: SiO 22The content is more than 70 percent, the fineness modulus FM ranges from 1.5 to 1.8, the maximum particle size of the particles is less than 2.36mm, and the content of the particles with the particle size of less than 75 mu m is 10 to 15 percent;
stone powder: CaCO3The content is more than 90 percent, and the content of particles with the particle diameter of less than 75 mu m is 90 to 95 percent;
pigment: is one or more of iron oxide yellow, iron oxide green and iron oxide red; certainly, blending is carried out according to the color requirement;
redispersible latex powder (EVA): the material is composed of a vinyl acetate-ethylene copolymer, model 5010, ash content is less than 10%, and solid content is more than 99.8%;
hydroxypropyl methylcellulose ether (HPMC): the brookfield viscosity is 10000 Pa.s-100000 Pa.s, the ash content is less than 6%, the hydroxypropyl content is 13-19%, the ash content is 2-5%, and the PH is 6-9;
zeolite powder: is clinoptilolite with whiteness of more than 80%, activity index of more than 75%, and fineness of more than 400m2The ammonium absorption value is 100mmol/100 g-150 mmol/100 g.
Experimental example 1:
preparing color dry-mixed mortar:
(1) preparing modified titanium dioxide:
the modified titanium dioxide prepared in example 1 was applied;
(2) preparation of modified mixture T-C
Raw materials (in parts by weight): 0.5 part of chitosan, 8 parts of isopropanol and ClCH2COOH 2 parts and modified titanium dioxide 87 parts;
b1, adding chitosan and a NaOH solution (the mass fraction is 60%) into a reaction container, wherein the mass ratio of the chitosan to the NaOH solution is 1:13, and the chitosan is alkalized in the NaOH solution;
b2, adding isopropanol and ClCH into the reaction vessel in sequence2COOH is stirred evenly and then placed for 3 hours at the temperature of 15 ℃; then heating to 65 ℃, and preserving heat for 2 hours; then using CH3Adjusting the PH value of COOH to be 8;
b3, adding the modified titanium dioxide prepared in the step (1) into a reaction container, uniformly stirring to obtain a mixture, filtering the mixture, and keeping a precipitate;
b4, using CH in turn for the precipitate obtained in the step B33CH2Washing with OH solution (70 wt%) and anhydrous methanol;
b5, drying at 50 ℃ after washing to obtain a modified mixture T-C;
(3) preparation of N, O carboxymethyl chitosan
Raw materials (in parts by weight): modified mixture T-C, water, CH3OCH3Solution (mass fraction is 75% -80%)
C1, dissolving the modified mixture T-C prepared in the step (2) in water at the temperature of 30 ℃ to obtain a solution a;
c2, adding CH to the solution a obtained in the step C13OCH3Carrying out precipitation reaction on the solution (the mass fraction is 80%), filtering after the reaction is finished, and keeping the precipitate;
c3 precipitation obtained in step C2 with anhydrous CH3CH2OH washing (for many times), then vacuum drying, controlling the molecular weight to 50000, and obtaining N, O carboxymethyl chitosan powder (substances with the molecular weight larger than 50000 can be returned to the step (2) to be mixed with raw material chitosan for use (namely, the mixed substances are used as chitosan), and the preparation of the modified mixture T-C is continuously carried out according to the step (2);
(4) preparation of mixture W
Raw materials (in parts by weight): 20 parts of white portland cement, 10 parts of modified mixture T-C and 0.5 part of N, O carboxymethyl chitosan;
uniformly mixing white portland cement, the modified mixture T-C obtained in the step (2) and the N, O carboxymethyl chitosan obtained in the step (3) according to the proportion, and controlling the screen residue of a 80-micron square-hole screen to be less than 1% to obtain a mixture W;
(5) preparation of finished product of colored dry-mixed mortar
Raw materials (in parts by weight): 80 parts of machine-made sand, 15 parts of mixture W, 1 part of stone powder, 5 parts of pigment (iron oxide yellow), 0.1 part of redispersible latex powder, 1.2 parts of hydroxypropyl methyl cellulose ether and 10 parts of zeolite powder;
and uniformly mixing the machine-made sand, the mixture W, the stone powder, the pigment, the redispersible latex powder, the hydroxypropyl methyl cellulose ether and the zeolite powder according to the proportion to obtain a finished product of the color dry-mixed mortar.
Experimental example 2:
preparing color dry-mixed mortar:
(1) preparing modified titanium dioxide:
the modified titanium dioxide prepared in example 2 was applied;
(2) preparation of modified mixture T-C
Raw materials (in parts by weight): 1.5 parts of chitosan, 12 parts of isopropanol and ClCH21 part of COOH and 90 parts of modified titanium dioxide;
b1, adding chitosan and a NaOH solution (the mass fraction is 50%) into a reaction container, wherein the mass ratio of the chitosan to the NaOH solution is 1:15, and the chitosan is alkalized in the NaOH solution;
b2, adding isopropanol and ClCH into the reaction vessel in sequence2COOH is stirred evenly and then placed for 2 hours at the temperature of 25 ℃; then heating to 70 ℃, and preserving heat for 1.5 h; then using CH3Adjusting the PH value of COOH to be 6;
b3, adding the modified titanium dioxide prepared in the step (1) into a reaction container, uniformly stirring to obtain a mixture, filtering the mixture, and keeping a precipitate;
b4, using CH in turn for the precipitate obtained in the step B33CH2Washing with OH solution (60 wt%) and anhydrous methanol;
b5, drying at the temperature of 70 ℃ after washing to obtain a modified mixture T-C;
(3) preparation of N, O carboxymethyl chitosan
Raw materials (in parts by weight): modified mixture T-C, water, CH3OCH3Solution (mass fraction is 75% -80%)
C1, dissolving the modified mixture T-C prepared in the step (2) in water at the temperature of 40 ℃ to obtain a solution a;
c2, adding CH to the solution a obtained in the step C13OCH3Carrying out precipitation reaction on the solution (the mass fraction is 80%), filtering after the reaction is finished, and keeping the precipitate;
c3 precipitation obtained in step C2 with anhydrous CH3CH2OH is washed for many times, then vacuum drying is carried out, the molecular weight is controlled to be 1000, and N, O carboxymethyl chitosan powder is obtained (substances with the molecular weight larger than 1000 can be returned to the step (2) to be mixed with the raw material chitosan for use (namely the mixed substances are used as chitosan), and the preparation of the modified mixture T-C is continuously carried out according to the step (2);
(4) preparation of mixture W
Raw materials (in parts by weight): 25 parts of white portland cement, 15 parts of modified mixture T-C and 0.1 part of N, O carboxymethyl chitosan;
uniformly mixing white portland cement, the modified mixture T-C obtained in the step (2) and the N, O carboxymethyl chitosan obtained in the step (3) according to the proportion, and controlling the screen residue of a 80-micron square-hole screen to be less than 1% to obtain a mixture W;
(5) preparation of finished product of colored dry-mixed mortar
Raw materials (in parts by weight): 90 parts of machine-made sand, 10 parts of mixture W, 10 parts of stone powder, 1 part of pigment (iron oxide yellow), 1 part of redispersible latex powder, 0.2 part of hydroxypropyl methyl cellulose ether and 15 parts of zeolite powder;
and uniformly mixing the machine-made sand, the mixture W, the stone powder, the pigment, the redispersible latex powder, the hydroxypropyl methyl cellulose ether and the zeolite powder according to the proportion to obtain a finished product of the color dry-mixed mortar.
Experimental example 3:
preparing color dry-mixed mortar:
(1) preparing modified titanium dioxide:
the modified titanium dioxide prepared in example 3 was applied;
(2) preparation of modified mixture T-C
Raw materials (in parts by weight): 0.8 part of chitosan, 11 parts of isopropanol and ClCH21.2 parts of COOH and 85 parts of modified titanium dioxide;
b1, adding chitosan and a NaOH solution (the mass fraction is 58%) into a reaction container, wherein the mass ratio of the chitosan to the NaOH solution is 1:10, and the chitosan is alkalized in the NaOH solution;
b2, adding isopropanol and ClCH into the reaction vessel in sequence2COOH is stirred evenly and then placed for 2.8 hours at the temperature of 18 ℃; then heating to 68 ℃, and preserving heat for 1.6 h; then using CH3Adjusting the pH value to 6.5 by COOH;
b3, adding the modified titanium dioxide prepared in the step (1) into a reaction container, uniformly stirring to obtain a mixture, filtering the mixture, and keeping a precipitate;
b4, using CH in turn for the precipitate obtained in the step B33CH2Washing with OH solution (mass fraction of 62%) and anhydrous methanol;
b5, drying at the temperature of 55 ℃ after washing to obtain a modified mixture T-C;
(3) preparation of N, O carboxymethyl chitosan
Raw materials (in parts by weight): modified mixture T-C, water, CH3OCH3Solution (mass fraction is 75% -80%)
C1, dissolving the modified mixture T-C prepared in the step (2) in water at the temperature of 32 ℃ to obtain a solution a;
c2, adding CH to the solution a obtained in the step C13OCH3Carrying out precipitation reaction on the solution (the mass fraction is 76%), filtering after the reaction is finished, and keeping the precipitate;
c3 precipitation obtained in step C2 with anhydrous CH3CH2OH is washed for many times, then vacuum drying is carried out, the molecular weight is controlled to be 10000, and N, O carboxymethyl chitosan powder is obtained (substances with the molecular weight larger than 10000 can be returned to the step (2) to be mixed with the raw material chitosan for use (namely the mixed substances are used as chitosan), and the preparation of the modified mixture T-C is continuously carried out according to the step (2);
(4) preparation of mixture W
Raw materials (in parts by weight): 22 parts of white portland cement, 14 parts of modified mixture T-C and 0.2 part of N, O carboxymethyl chitosan;
uniformly mixing white portland cement, the modified mixture T-C obtained in the step (2) and the N, O carboxymethyl chitosan obtained in the step (3) according to the proportion, and controlling the screen residue of a 80-micron square-hole screen to be less than 1% to obtain a mixture W;
(5) preparation of finished product of colored dry-mixed mortar
Raw materials (in parts by weight): 82 parts of machine-made sand, 12 parts of mixture W, 8 parts of stone powder, 4 parts of pigment (iron oxide green), 0.3 part of redispersible latex powder, 1 part of hydroxypropyl methyl cellulose ether and 14 parts of zeolite powder;
and uniformly mixing the machine-made sand, the mixture W, the stone powder, the pigment, the redispersible latex powder, the hydroxypropyl methyl cellulose ether and the zeolite powder according to the proportion to obtain a finished product of the color dry-mixed mortar.
Experimental example 4:
preparing color dry-mixed mortar:
(1) preparing modified titanium dioxide:
the modified titanium dioxide prepared in example 4 was applied;
(2) preparation of modified mixture T-C
Raw materials (in parts by weight): 1.2 parts of chitosan, 9 parts of isopropanol and ClCH21.8 parts of COOH and 86 parts of modified titanium dioxide;
b1, adding chitosan and a NaOH solution (the mass fraction is 52%) into a reaction container, wherein the mass ratio of the chitosan to the NaOH solution is 1:12, and the chitosan is alkalized in the NaOH solution;
b2, adding isopropanol and ClCH into the reaction vessel in sequence2COOH is stirred evenly and then placed for 2.2 hours at the temperature of 22 ℃; then heating to 66 ℃, and preserving heat for 1.8 h; then using CH3Adjusting the pH value to 7.5 by COOH;
b3, adding the modified titanium dioxide prepared in the step (1) into a reaction container, uniformly stirring to obtain a mixture, filtering the mixture, and keeping a precipitate;
b4, the stepThe precipitate obtained from B3 was successively treated with CH3CH2Washing with OH solution (68% by mass) and anhydrous methanol;
b5, drying at the temperature of 65 ℃ after washing to obtain a modified mixture T-C;
(3) preparation of N, O carboxymethyl chitosan
Raw materials (in parts by weight): modified mixture T-C, water, CH3OCH3Solution (mass fraction is 75% -80%)
C1, dissolving the modified mixture T-C prepared in the step (2) in water at the temperature of 38 ℃ to obtain a solution a;
c2, adding CH to the solution a obtained in the step C13OCH3Carrying out precipitation reaction on the solution (the mass fraction is 78%), filtering after the reaction is finished, and keeping the precipitate;
c3 precipitation obtained in step C2 with anhydrous CH3CH2OH washing (for many times), then vacuum drying, controlling the molecular weight to be 40000, obtaining N, O carboxymethyl chitosan powder (substances with the molecular weight larger than 40000 can be returned to the step (2) to be mixed with the raw material chitosan for use (namely, the mixed substances are used as chitosan), and the preparation of the modified mixture T-C is continuously carried out according to the step (2);
(4) preparation of mixture W
Raw materials (in parts by weight): 24 parts of white portland cement, 11 parts of modified mixture T-C and 0.4 part of N, O carboxymethyl chitosan;
uniformly mixing white portland cement, the modified mixture T-C obtained in the step (2) and the N, O carboxymethyl chitosan obtained in the step (3) according to the proportion, and controlling the screen residue of a 80-micron square-hole screen to be less than 1% to obtain a mixture W;
(5) preparation of finished product of colored dry-mixed mortar
Raw materials (in parts by weight): 88 parts of machine-made sand, 14 parts of mixture W, 3 parts of stone powder, 2 parts of pigment, 0.8 part of redispersible latex powder, 0.4 part of hydroxypropyl methyl cellulose ether and 11 parts of zeolite powder;
and uniformly mixing the machine-made sand, the mixture W, the stone powder, the pigment, the redispersible latex powder, the hydroxypropyl methyl cellulose ether and the zeolite powder according to the proportion to obtain a finished product of the color dry-mixed mortar.
Experimental example 5:
preparing color dry-mixed mortar:
(1) preparing modified titanium dioxide:
the modified titanium dioxide prepared in example 5 was applied;
(2) preparation of modified mixture T-C
Raw materials (in parts by weight): 1 part of chitosan, 10 parts of isopropanol and ClCH21.5 parts of COOH and 88 parts of modified titanium dioxide;
b1, adding chitosan and a NaOH solution (the mass fraction is 50-60%) into a reaction container, wherein the mass ratio of the chitosan to the NaOH solution is 1:14, and the chitosan is alkalized in the NaOH solution;
b2, adding isopropanol and ClCH into the reaction vessel in sequence2COOH is stirred evenly and then placed for 1.5 hours at the temperature of 20 ℃; then heating to 67 ℃, and preserving heat for 1.8 h; then using CH3Adjusting the PH value to 7 by COOH;
b3, adding the modified titanium dioxide prepared in the step (1) into a reaction container, uniformly stirring to obtain a mixture, filtering the mixture, and keeping a precipitate;
b4, using CH in turn for the precipitate obtained in the step B33CH2Washing with OH solution (65% by weight) and anhydrous methanol;
b5, drying at the temperature of 60 ℃ after washing to obtain a modified mixture T-C;
(3) preparation of N, O carboxymethyl chitosan
Raw materials (in parts by weight): modified mixture T-C, water, CH3OCH3Solution (mass fraction is 75% -80%)
C1, dissolving the modified mixture T-C prepared in the step (2) in water with the temperature of 35 ℃ to obtain a solution a;
c2, adding CH to the solution a obtained in the step C13OCH3Carrying out precipitation reaction on the solution (the mass fraction is 77%), filtering after the reaction is finished, and keeping the precipitate;
c3 precipitation obtained in step C2 with anhydrous CH3CH2OH washing (for many times), then vacuum drying, controlling the molecular weight to be 30000, obtaining N, O carboxymethyl chitosan powder (substances with the molecular weight larger than 30000 can be returned to the step (2) to be mixed with the raw material chitosan for use (namely, the mixed substances are used as chitosan), and the preparation of the modified mixture T-C is continuously carried out according to the step (2));
(4) preparation of mixture W
Raw materials (in parts by weight): 23 parts of white portland cement, 12 parts of modified mixture T-C and 0.3 part of N, O carboxymethyl chitosan;
uniformly mixing white portland cement, the modified mixture T-C obtained in the step (2) and the N, O carboxymethyl chitosan obtained in the step (3) according to the proportion, and controlling the screen residue of a 80-micron square-hole screen to be less than 1% to obtain a mixture W;
(5) preparation of finished product of colored dry-mixed mortar
Raw materials (in parts by weight): 85 parts of machine-made sand, 12 parts of mixture W, 6 parts of stone powder, 3 parts of pigment (iron oxide red), 0.5 part of redispersible latex powder, 0.8 part of hydroxypropyl methyl cellulose ether and 12 parts of zeolite powder;
and uniformly mixing the machine-made sand, the mixture W, the stone powder, the pigment, the redispersible latex powder, the hydroxypropyl methyl cellulose ether and the zeolite powder according to the proportion to obtain a finished product of the color dry-mixed mortar.
3. The color dry-mixed mortar prepared in experimental examples 1 to 5 was subjected to construction:
1. preparing cement mortar:
water was directly added to the color dry-mixed mortar prepared in experimental example 1, and the added water was added in a weight ratio (color dry-mixed mortar: water: 150: 1000);
water was directly added to the color dry-mixed mortar prepared in experimental example 2, and the added water was added in a weight ratio (color dry-mixed mortar: water: 200: 1000);
water was directly added to the color dry-mixed mortar prepared in experimental example 3, and the added water was added in a weight ratio (color dry-mixed mortar: water: 165: 1000);
water was directly added to the color dry-mixed mortar prepared in experimental example 4, and the added water was added in a weight ratio (color dry-mixed mortar: water: 185: 1000);
water was directly added to the color dry-mixed mortar prepared in experimental example 5, and the added water was added in a weight ratio (color dry-mixed mortar: water: 175: 1000);
2. construction:
during construction, if the construction is carried out according to the traditional color mortar, the wall surface must be coated with finish paint before construction, but the color dry-mixed mortar prepared in the experimental examples 1-5 of the invention has the functions of water resistance and saltpetering resistance, can be directly primed and plastered according to the operation of the traditional plastering mortar, is extremely convenient to construct, can reduce two construction procedures (a finish paint coating procedure and a bottom layer plastering mortar procedure) during construction, and can improve the construction efficiency by 200 percent.
The cement mortar prepared from the color dry-mixed mortar prepared in the experimental examples 1 to 5 has good workability and convenient consistency adjustment, when the mortar consistency is 90mm to 100mm, the color of the mortar construction wall surface is bright, the color main body can still be well expressed in a wet state, and the bleeding phenomenon does not occur in the construction;
the colored dry-mixed mortar prepared in the experimental examples 1 to 5 and the colored mortar (stuccoo color mortar produced by Chengdu Leili paint particle Co., Ltd.) in the prior art are used as comparative examples, construction is carried out under the same conditions, the performance after construction is tested according to GB 50210 and 2001 'quality acceptance criteria for architectural decoration and finishing engineering', and the comparative results are shown in the following table 2:
the cement mortar prepared from the color dry-mixed mortar prepared in the experimental examples 1 to 5 has good cohesiveness and smooth and soft plastering surface.
TABLE 2 construction Properties comparison Table
As can be seen from table 1:
the compressive strength of the color dry-mixed mortar prepared in the experimental examples 1 to 5 after 7d is higher than that of the color mortar prepared in the comparative example under the same conditions;
the color dry-mixed mortar prepared in the experimental examples 1 to 5 has no obvious difference between the wall color at 28d and the wall color at 3d, because the color dry-mixed mortar prepared in the experimental examples 1 to 5 of the invention basically does not absorb water after 1 hour, and the surface moisture evaporates quickly; whereas the wall in the comparative example turned white in color.
And thirdly, the 28d compressive strength and tensile strength of the color dry-mixed mortar prepared in experimental examples 1 to 5 are not changed from those of the dry-mixed mortar in the comparative example, the weather resistance is improved by 50 to 100 percent, no visible saltpetering phenomenon, no powder falling, no hollowing and cracking phenomenon are caused, the stain resistance is obviously improved, and the grade 1 is achieved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.
Claims (10)
1. A preparation method of modified titanium dioxide is characterized by comprising the following steps: the method comprises the following steps:
a1, adding butyl titanate into a reactor, and gasifying the butyl titanate at the temperature of 40-130 ℃ under the protection of inert gas;
a2, adding water into a reactor, and reacting at 500-550 ℃ and 0.5 × 105Pa-1.5×105Pa, inert gas protection to obtain nano TiO2；
A3, and the nanometer TiO obtained in the step A22Placing the mixture in an inert gas atmosphere to reduce the temperature to 20-25 ℃;
a4, cooling the TiO obtained in the step A32And (4) carrying out screen analysis to obtain a finished product of the modified titanium dioxide.
2. The preparation method of the modified titanium dioxide according to claim 1, characterized in that: in the step A4, the screening is to cool the TiO obtained in the step A32Placing in a 45 μm round hole sieve, and controlling TiO2The content is more than 98 percent, the screen residue is less than 0.01 percent, the volatile matter at 105 ℃ is less than 0.05 percent, and the L value range is 98.5-100.
3. The preparation method of the modified titanium dioxide according to claim 1, characterized in that: in the step A2, the mass ratio of the water to the butyl titanate is 2: 1-20:1.
4. The preparation method of the modified titanium dioxide according to claim 1, characterized in that: in the step A2, the flow rate of the inert gas is 0.5L/min-1.2L/min, the flow rate of the water vapor is 1L/min-2L/min, and the reaction time is 20min-35 min.
5. The preparation method of the modified titanium dioxide according to claim 4, characterized in that: in the step A2, the flow rate of the inert gas is 1L/min, the flow rate of the water vapor is 1L/min, and the reaction time is 30 min.
6. The preparation method of the modified titanium dioxide according to any one of claims 1 to 5, characterized in that: in the step A1 and the step A2, the inert gas is N2。
7. The preparation method of the modified titanium dioxide according to claim 6, which is characterized in that: in the step A3, the inert gas is CO2。
8. The method for preparing modified titanium dioxide according to claim 7, wherein in step A2, the pressure is 0.5 × 105Pa-2×105Pa。
9. A modified titanium dioxide prepared by the preparation method of any one of claims 1 to 8.
10. Use of the modified titanium dioxide prepared by the preparation method according to any one of claims 1 to 8 in preparing a color dry-mixed mortar.
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