CN107488276B - Preparation method of nano calcium carbonate for high-thixotropy PVC paste - Google Patents
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Abstract
The invention discloses a preparation method of nano calcium carbonate for high thixotropy PVC paste, which comprises the steps of adjusting the specific gravity of lime milk to 1.06-1.08, adding a crystal form control agent, and introducing into a bubbling carbonation reaction kettle; introducing kiln gas for carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 60-70%, gradually reducing the carbon dioxide concentration to 30-35% after 20-30min of carbonation reaction, and when the pH of the reaction solution is reduced to 7.0, ending the carbonation reaction to obtain nano calcium carbonate suspension; heating to 75-85 ℃, adding a compound surface treating agent, and stirring to complete surface modification to obtain a modified nano calcium carbonate suspension; and then carrying out filter pressing, dehydration, drying and crushing to obtain the nano calcium carbonate product for the PVC paste. The nano calcium carbonate prepared by the invention has the advantages of high thixotropy, lower viscosity, good dispersibility, lower moisture absorption and the like, and when the nano calcium carbonate is applied to filling of the PVC paste of the automobile chassis coating, the thixotropy and the anti-sagging performance of the PVC paste can be improved, and the problem that the treating agent is yellowed and affects the hue of the automobile chassis coating can be solved.
Description
Technical Field
The invention relates to the technical field of inorganic material modification, in particular to a preparation method of nano calcium carbonate for high-thixotropy PVC paste.
Background
PVC paste is used in the form of a paste for PVC, which is commonly referred to as a plastisol, a unique paste form of PVC plastic in the unformed state. The PVC paste resin has the advantages of simple preparation process, stable performance, easy control, convenient use, excellent product performance, good chemical stability, easy coloring mechanical strength and the like, and is widely applied to manufacturing artificial leather, vinyl toys, soft trademarks, wallpaper, paint coatings, foamed plastics and the like. The nano calcium carbonate is used as a common inorganic filler in PVC paste, and the quality of the nano calcium carbonate has important influence on the performance of the PVC paste. A high-quality nano calcium carbonate should have the following properties:
high thixotropy
A high-quality nano calcium carbonate should impart good thixotropy to PVC paste. In order to obtain a smooth coating with a high-quality appearance, it is necessary to maintain sufficient flatness during the use of the coating or during the drying/curing of the coating, to improve thixotropy while reducing the occurrence of irregular surfaces of the coating, and to help avoid sagging problems.
Low viscosity
The addition of inorganic fillers to PVC pastes generally causes a considerable increase in the viscosity of the system, which is disadvantageous for coating processing and construction. Thus, the addition of a good quality filler should not raise the viscosity of the system too much.
Third, dispersibility
The dispersibility of the inorganic filler in the coating is an important index for judging the quality of the filler. The dispersion condition of calcium carbonate in PVC paste is influenced by more factors, and the calcium carbonate with cubic morphology and narrow particle size distribution can be generally selected to obtain better dispersion.
Fourth, higher whiteness
The whiteness of the nano calcium carbonate should be 85-95% generally, but the whiteness is not necessarily too high, and the whiteness possibly affects the covering power of other pigments.
Fifth, lower oil absorption value
The oil absorption value of the nano calcium carbonate should be within a reasonable range, and if the oil absorption value is too low, the mechanical property of the product is reduced, and if the oil absorption value is too high, the flexibility of the product is insufficient, and the cost is increased.
In recent years, many studies have been made on nano calcium carbonate, but the nano calcium carbonate generally has the problems of low thixotropy, high viscosity, easy agglomeration and the like, and the quality of the nano calcium carbonate is difficult to meet the requirements of PVC paste fillers.
Disclosure of Invention
The invention provides a preparation method of high-thixotropy nano calcium carbonate for PVC paste, aiming at the problems of the existing nano calcium carbonate filler for PVC paste. The nano calcium carbonate prepared by the method not only can solve the problems of dispersibility, fluidity, glossiness and the like of PVC paste in the application of automobile chassis paint, but also can obviously improve the thixotropy.
The invention is realized based on the following principles:
a carbonation stage:
Ca(OH)2+CO2=CaCO3
in the initial stage of carbonation, the mass transfer rate is increased by increasing the concentration of carbon dioxide, the nucleation rate is accelerated, the growth of calcium carbonate particles in the stage is slowed down, and the nucleation size is uniform. After the carbonation reaction is carried out for 20min, the concentration of the carbon dioxide is gradually reduced, so that the calcium carbonate particles slowly grow, and the crystal morphology is more regular.
Following the carbonation process by pH test, obtaining a specific surface area of 20-30m by adding a crystal form controlling agent2Cubic calcium carbonate suspension in g.
Surface treatment:
the selected nano calcium carbonate surface treating agent is compounded by a high molecular copolymer and fatty acid, wherein the high molecular polymer is a block copolymer which simultaneously has a hard chain and a soft chain. The soft segments and the soft segments of the fatty acids play a major role in the development of high shear forces, which results in lower viscosity of the PVC paste system. Under the condition of low shearing or no shearing action, the polarity difference between the hard chain segment and the soft chain segment is large, phase separation is generated, and the system is quickly recovered to a high-viscosity state.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of nano calcium carbonate for high-thixotropy PVC paste comprises the following steps:
(1) regulating the specific gravity of the lime milk to 1.06-1.08, adding a crystal form control agent, and then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 22-28 ℃, introducing kiln gas to perform carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 60-70%, gradually reducing the carbon dioxide concentration to 30-35% after 20-30min of carbonation reaction, and finishing the carbonation reaction when the pH of reaction liquid is reduced to 7.0 to obtain nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 75-85 ℃, adding a compound surface treating agent, stirring for 30-60min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent is prepared by compounding fatty acid saponification liquid and a high-molecular copolymer, wherein the high-molecular copolymer comprises one or more of styryl phenol polyoxyethylene ether, styryl phenol polyoxyethylene ether ammonium sulfate, styrene and butadiene block copolymer;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a drying oven at the temperature of 100-110 ℃, and crushing to obtain the nano calcium carbonate product for PVC paste.
Further, the addition amount of the crystal form control agent is 1.0-2.0% of the dry weight of the calcium carbonate.
Further, the crystal form control agent is a non-reducing saccharide and metal salt compound; the non-reducing saccharide is sucrose and/or galactose; the metal salt is Al2(SO4)3And/or MgCl2。
Further, the non-reducing saccharides account for 30-40% of the weight of the crystal form control agent, and the metal salt compound accounts for 60-70% of the weight of the crystal form control agent.
Further, the fatty acid saponification liquid is a saturated fatty acid saponification liquid with 18-22 carbon atoms.
Furthermore, the weight ratio of the fatty acid saponification liquid in the compound surface treating agent is 60-70%, and the weight ratio of the high molecular copolymer is 30-40%.
Further, the dosage of the compound surface treating agent is 3.0-4.0% of the dry weight of the calcium carbonate.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the nano calcium carbonate prepared by the method has the advantages of high thixotropy, lower viscosity, good dispersibility, lower moisture absorption and the like, and can be used as an excellent filling filler for PVC paste.
2. When the nano calcium carbonate prepared by the invention is applied to filling of the PVC paste of the automobile chassis coating, the thixotropy and the anti-sagging performance of the PVC paste can be improved, and the problem that the treating agent is yellowed and affects the hue of the automobile chassis coating can be solved.
3. The invention has simple and feasible process, low production cost and better economic and social benefits.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
A preparation method of nano calcium carbonate for high-thixotropy PVC paste comprises the following steps:
(1) adjusting the specific weight of lime milk to 1.06, adding a crystal form control agent which is 1.0 percent of the dry weight of calcium carbonate, wherein the crystal form control agent consists of sucrose and MgCl with the mass ratio of 4:62Composition of，Then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 25 ℃, introducing kiln gas to carry out carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 66%, gradually reducing the carbon dioxide concentration to 33% after 20min of carbonation reaction, and finishing the carbonation reaction when the pH of a reaction solution is reduced to 7.0 to obtain a nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 75 ℃, adding a compound surface treating agent accounting for 3.3 percent of the dry weight of the calcium carbonate, stirring for 60min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent is prepared from the following components in percentage by mass of 3: 2 sodium stearate and styrylphenol polyoxyethylene ether;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a drying oven at 110 ℃, and crushing to obtain the nano calcium carbonate product for the PVC paste.
Example 2
A preparation method of nano calcium carbonate for high-thixotropy PVC paste comprises the following steps:
(1) adjusting the specific weight of lime milk to 1.070, adding a crystal form control agent which is 1.5 percent of the dry weight of calcium carbonate, wherein the crystal form control agent consists of galactose and Al2(SO4)3 in a mass ratio of 3:7，Then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 23 ℃, introducing kiln gas to perform carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 60%, gradually reducing the carbon dioxide concentration to 30% after the carbonation reaction is carried out for 25min, and finishing the carbonation reaction when the pH of the reaction solution is reduced to 7.0 to obtain a nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 80 ℃, adding a compound surface treating agent accounting for 3.0 percent of the dry weight of the calcium carbonate, stirring for 30min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent is prepared from the following components in percentage by mass: 3 sodium stearate and styrylphenol polyoxyethylene ether ammonium sulfate;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a 115 ℃ oven, and crushing to obtain the nano calcium carbonate product for PVC paste.
Example 3
A preparation method of nano calcium carbonate for high-thixotropy PVC paste comprises the following steps:
(1) adjusting the specific weight of lime milk to 1.08, adding a crystal form control agent which is 2.0 percent of the dry weight of calcium carbonate, wherein the crystal form control agent comprises 10 percent of cane sugar, 30 percent of galactose and 70 percent of Al in percentage by mass2(SO4)3Composition of，Then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 26 ℃, introducing kiln gas to perform carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 70%, gradually reducing the carbon dioxide concentration to 30% after 20min of carbonation reaction, and when the pH of the reaction solution is reduced to 7.0, finishing the carbonation reaction to obtain a nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 85 ℃, adding a compound surface treating agent accounting for 4.0 percent of the dry weight of the calcium carbonate, stirring for 60min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent consists of 65 mass percent of sodium stearate and 35 mass percent of styrene and butadiene block copolymer;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a 100 ℃ oven, and crushing to obtain the nano calcium carbonate product for PVC paste.
Example 4
A preparation method of nano calcium carbonate for high-thixotropy PVC paste comprises the following steps:
(1) adjusting the specific weight of lime milk to 1.065, and adding a crystal form control agent which is 1.8 percent of the dry weight of calcium carbonate, wherein the crystal form control agent consists of 30 percent of sucrose and 20 percent of Al in percentage by mass2(SO4)3And 50% MgCl2Composition of，Then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 26 ℃, introducing kiln gas to perform carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 70%, gradually reducing the carbon dioxide concentration to 30% after 20min of carbonation reaction, and when the pH of the reaction solution is reduced to 7.0, finishing the carbonation reaction to obtain a nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 80 ℃, adding a compound surface treating agent accounting for 3.5 percent of the dry weight of the calcium carbonate, stirring for 40min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent consists of 60 mass percent of myristic acid, 20 mass percent of styryl phenol polyoxyethylene ether and 20 mass percent of styrene-butadiene block copolymer;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a drying oven at 105 ℃, and crushing to obtain the nano calcium carbonate product for PVC paste.
Example 5
A preparation method of nano calcium carbonate for high-thixotropy PVC paste comprises the following steps:
(1) the specific weight of the lime milk is adjusted to 1.075, a crystal form control agent which is 1.5 percent of the dry weight of the calcium carbonate is added,the crystal form control agent consists of 35% of galactose and 65% of Al in percentage by mass2(SO4)3Composition of，Then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 25 ℃, introducing kiln gas to carry out carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 66%, gradually reducing the carbon dioxide concentration to 33% after the carbonation reaction is carried out for 25min, and finishing the carbonation reaction when the pH of the reaction solution is reduced to 7.0 to obtain nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 75 ℃, adding a compound surface treating agent accounting for 3.0 percent of the dry weight of the calcium carbonate, stirring for 30min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent consists of 70 percent of myristic acid and 30 percent of styrene phenol polyoxyethylene ether ammonium sulfate in percentage by mass;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a drying oven at 110 ℃, and crushing to obtain the nano calcium carbonate product for the PVC paste.
Comparative example 1
(1) Adjusting the specific weight of lime milk to 1.075, and adding a crystal form control agent which is 1.5 percent of the dry weight of calcium carbonate, wherein the crystal form control agent comprises 35 percent of galactose and 65 percent of Al in percentage by mass2(SO4)3Then introducing the mixture into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 25 ℃, introducing kiln gas to perform carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 66%, gradually reducing the carbon dioxide concentration to 33% after the carbonation reaction is carried out for 25min, and finishing the carbonation reaction when the pH of the reaction liquid is reduced to 7.0 to obtain nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 75 ℃, adding a sodium stearate surface treating agent accounting for 3.0 percent of the dry weight of the calcium carbonate, stirring for 30min, and finishing surface modification to obtain a modified nano calcium carbonate suspension;
(4) and (3) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a drying oven at 110 ℃, and crushing to obtain the nano calcium carbonate product for the PVC paste.
The nano calcium carbonate prepared by the embodiment of the invention is applied to PVC paste for preparing automobile chassis coating, wherein the formula of the PVC paste for the automobile chassis coating is shown in Table 1.
Table 1: PVC paste formula table of automobile chassis coating
| Name (R) | Number of parts |
| PVC resin | 28 |
| DOP | 35 |
| Calcium stearate | 3 |
| Nano calcium carbonate | 27 |
| Calcium oxide | 2 |
| N, N dimethyl acetamide | 5 |
The automobile chassis coatings prepared in the examples and the comparative examples of the invention are subjected to performance tests, and the test results are shown in table 2.
Oil absorption value: accurately weighing 5g of nano calcium carbonate product, placing the nano calcium carbonate product on a glass plate, dropwise adding DOP (dioctyl phthalate) and continuously turning over by using a knife, wherein the sample is dispersed at first, and then gradually forming a cluster until the whole cluster is completely infiltrated by the DOP, namely the end point.
Wherein X represents an oil absorption value; m1 represents the mass g of the dropping bottle and DOP before dropping DOP; m2 represents the mass g of the dropping bottle and DOP after dropping DOP; m represents the sample mass g.
Thixotropy testing: PVC paste samples were prepared according to the formulation shown in Table 1, and the samples were tested for viscosity at high shear (100 rpm) and low shear (5 rpm) using a Brookfield viscometer, the ratio of low and high shear viscosities being thixotropy.
Area of the thixotropic ring: thixotropic ring area was measured on the PVC paste samples using a rotational rheometer.
Yield value: the yield value was measured on the PVC paste sample using a rotational rheometer.
Table 2: PVC paste performance test result of automobile chassis coating
| Sample name | The oil absorption value of the oil-absorbing material, DOP/ 100gCaCO3 | dispersibility | Low shear Viscosity- 104, cp | High shear viscosity Degree/104, cp | Low and high Shear ratio | Yield and yield The value of the one or more of, Pa | thixotropic ring surface Product of Pa/s |
| Example 1 | 37.6 | Good, no bright Revealing particles | 21.6 | 2.56 | 8.43 | 201.4 | 165.4 |
| Example 2 | 39.2 | Good, no bright Revealing particles | 23.6 | 2.48 | 8.48 | 194.3 | 187.2 |
| Example 3 | 40.1 | Good, no bright Revealing particles | 22.4 | 2.21 | 10.13 | 220.1 | 201.6 |
| Example 4 | 37.3 | Good, no bright Revealing particles | 26.1 | 2.38 | 9.74 | 208.1 4 | 214.3 |
| Example 5 | 38.1 | Good, no bright Revealing particles | 25.8 | 2.51 | 8.98 | 211.9 | 208.9 |
| Comparative example 1 | 45.3 | Good, no bright Revealing particles | 14.3 | 2.91 | 5.09 | 50.8 | 637.2 |
From the test results in table 2, the examples showed higher viscosity at low shear and lower viscosity at high shear, compared with the comparative examples, which indicates that the system was greatly affected by shear force, i.e. thixotropy was better in each example. The yield values of the comparative examples and comparative examples were found to be significantly greater for each example than for the comparative examples, indicating that the sag resistance of each example is significantly better than the comparative examples. The thixotropic ring area of each example is much smaller than the thixotropic ring area of the comparative example in view of the thixotropic ring area, which indicates that the energy required for the conversion process of each example from sol to gel is less and also indicates that the thixotropy of the system of each example is better than that of the comparative example. This is because the examples use a compound having both soft and hard segments in the surface treatment, and the soft segment of fatty acid play a major role in the high shear force, so that the PVC paste system exhibits a low viscosity. Under the condition of low shearing or no shearing action, the polarity difference between the hard chain segment and the soft chain segment is large, phase separation is generated, and the system is quickly recovered to a high-viscosity state. The comparative examples, however, were surface treated with sodium stearate having soft segments only, and the thixotropic effect was not increased.
The nano calcium carbonate product prepared by the invention is cubic, has good dispersibility, can meet the conventional requirements of filling PVC paste in the application of automobile chassis coatings, can also obviously improve the thixotropy, and has very wide market prospect.
Claims (1)
1. A preparation method of nano calcium carbonate for high-thixotropy PVC paste is characterized by comprising the following steps: the method comprises the following steps:
(1) regulating the specific gravity of the lime milk to 1.06-1.08, adding a crystal form control agent, and then introducing into a bubbling carbonation reaction kettle;
(2) regulating the temperature of lime milk to 22-28 ℃, introducing kiln gas for carbonation reaction, wherein the volume concentration of kiln gas carbon dioxide is 60-70%, gradually reducing the carbon dioxide concentration to 30-35% after 20-30min of carbonation reaction, and when the pH of the reaction solution is reduced to 7.0, finishing the carbonation reaction to obtain nano calcium carbonate suspension;
(3) heating the obtained nano calcium carbonate suspension to 75-85 ℃, adding a compound surface treating agent, stirring for 30-60min, and finishing surface modification to obtain a modified nano calcium carbonate suspension; the compound surface treating agent is prepared by compounding fatty acid saponification liquid and a high-molecular copolymer, wherein the high-molecular copolymer comprises one or more of styryl phenol polyoxyethylene ether, styryl phenol polyoxyethylene ether ammonium sulfate, styrene and butadiene block copolymer;
(4) carrying out filter pressing dehydration on the modified nano calcium carbonate suspension, drying in a drying oven at the temperature of 100-110 ℃, and crushing to obtain a nano calcium carbonate product for PVC paste;
the addition amount of the crystal form control agent is 1.0-2.0% of the dry weight of calcium carbonate;
the crystal form control agent is a compound of non-reducing saccharides and metal salts; the non-reducing saccharide is sucrose and/or galactose; the metal salt is Al2(SO4)3And/or MgCl2；
The fatty acid saponification liquid is saturated fatty acid saponification liquid with 18-22 carbon atoms;
the weight ratio of the fatty acid saponification liquid in the compound surface treating agent is 60-70%, and the weight ratio of the high molecular copolymer is 30-40%;
the non-reducing saccharides account for 30-40% of the weight of the crystal form control agent, and the metal salt compound accounts for 60-70% of the weight of the crystal form control agent;
the dosage of the compound surface treating agent is 3.0-4.0% of the dry weight of the calcium carbonate.
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| CN112724708B (en) * | 2021-01-11 | 2021-09-28 | 广西华纳新材料科技有限公司 | Surface treatment method of nano calcium carbonate for impact-resistant automobile chassis coating |
| CN112960685A (en) * | 2021-03-04 | 2021-06-15 | 安徽省宣城市华纳新材料科技有限公司 | Preparation method of nano calcium carbonate for filling hard PVC (polyvinyl chloride) |
| CN113980491A (en) * | 2021-11-19 | 2022-01-28 | 广西华纳新材料科技有限公司 | Preparation method of nano calcium carbonate for anti-sagging PVC (polyvinyl chloride) plastisol |
| CN114291836B (en) * | 2021-12-31 | 2023-09-19 | 连州市凯恩斯纳米材料有限公司 | Calcium carbonate crystal form control agent, application thereof and preparation method of cubic calcium carbonate |
| CN115181432B (en) * | 2022-08-04 | 2023-05-26 | 安徽省宣城市华纳新材料科技有限公司 | Surface treatment method for improving thixotropic property of filled PVC paste by nano calcium carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| HUE025587T2 (en) * | 2011-11-04 | 2016-04-28 | Omya Int Ag | Process for the purification of water and/or dewatering of sludges and/or sediments using a surface-treated calcium carbonate |
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| CN105217673B (en) * | 2015-10-21 | 2018-01-09 | 常山县南方碳酸钙有限公司 | A kind of preparation method of high thixotropic silicone adhesive special-purpose nanometer activated Calcium carbonate |
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