Modified composite powder for PVC (polyvinyl chloride) homogeneous coiled material floor as well as preparation method and application of modified composite powder

Abstract

The invention belongs to the technical field of inorganic nonmetal powder, and provides modified composite powder for a PVC homogeneous coiled material floor as well as a preparation method and application of the modified composite powder. The preparation method comprises the following steps: mixing blocky white mica, blocky wollastonite and a polymeric dispersant solution, grinding in an airflow mill, and carrying out cyclone classification on a grinding product to obtain composite powder; and mixing the composite powder with a surface modifier solution, and carrying out stirring modification. According to the method, the muscovite concentrate and the wollastonite concentrate are calcined, so that organic matters are reduced, and the purity of minerals and the whiteness of the composite powder are improved; a fluidized bed jet mill is used for grinding, and a betaine type amphoteric dispersant is used for dispersing, so that the layered structure of muscovite and the needle-shaped structure of wollastonite are ensured, the elasticity required by the product is improved, and the wear resistance, acid and alkali resistance, scalding resistance and low shrinkage of the product are ensured; the surface modifier is adopted to modify the composite powder, so that the compatibility of the composite powder and the PVC resin can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of inorganic non-metallic powders, and particularly to a modified composite powder for PVC homogeneous coil flooring, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous development of the country, the improvement of people's living standards and the increasing demand for material quality, the application requirements for polyvinyl chloride (PVC) homogeneous coil flooring in the fields of home decoration, shopping malls, stations, hospitals, etc. are getting higher and higher. Especially in crowded places such as shopping malls, stations, and hospitals, the requirements for this kind of flooring are more stringent in terms of mechanical properties, wear resistance, weather resistance, heat resistance, low shrinkage, etc. The filler used in the traditional method for producing PVC homogeneous coil flooring is calcium carbonate. Although adding single calcium carbonate can reduce production costs and have certain wear resistance and mechanical properties, it cannot meet the comprehensive requirements of the material for wear resistance grade, weather resistance, heat resistance, low shrinkage, etc.

[0003] Therefore, in order to improve the various indicators of PVC homogeneous coil flooring, developing a new type of functional inorganic non-metallic composite powder has become a new research hotspot. Summary of the Invention

[0004] The purpose of the present invention is to provide a modified composite powder for PVC homogeneous coil flooring, a preparation method thereof, and an application thereof in order to overcome the deficiencies of the prior art.

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a preparation method of a modified composite powder for PVC homogeneous coil flooring, comprising the following steps:

[0007] 1) Calcining and subjecting mica concentrate to two-stage jaw crushing in sequence to obtain massive mica;

[0008] Calcining and subjecting wollastonite concentrate to two-stage jaw crushing in sequence to obtain massive wollastonite;

[0009] 2) Mixing the massive mica, massive wollastonite and a polymer dispersant solution, and grinding the mixture in a jet mill. The grinding product is subjected to cyclone classification to obtain a composite powder;

[0010] 3) Mixing the composite powder with a surface modifier solution, and performing stirring modification to obtain a modified composite powder for PVC homogeneous coil flooring.

[0011] Preferably, the mass content of muscovite in the muscovite concentrate is ≥95%, the mass content of calcium silicate in the wollastonite concentrate is ≥95%, the calcination temperature of the muscovite concentrate and the wollastonite concentrate is independently 300-400°C, and the calcination time is independently 60-90 min.

[0012] Preferably, the mass ratio of massive muscovite to massive wollastonite is 1:3-6; the mass of the polymer dispersant is 0.3-0.7% of the total mass of massive muscovite and massive wollastonite; the polymer dispersant is a betaine-type amphoteric dispersant.

[0013] Preferably, the polymer dispersant solution is obtained by mixing the polymer dispersant with water at 80-85°C, and the polymer dispersant is one or more of carboxybetaine, sulfobetaine, alkyl betaine, and phosphate ester betaine.

[0014] Preferably, the jet mill is a fluidized bed jet mill; during the grinding process, the feeding rate is 1.5-2.5 t / h, the grinding pressure is 0.6-0.8 MPa, the nozzle diameter is 1-3 mm, the air flow rate is 300-350 m / s, the grinding time is 60-75 min; the rotational speed of the turbine classifier for cyclone classification is 1000-1300 r / min.

[0015] Preferably, the surface modifier is isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent and γ-(methacryloyloxy)propyltrimethoxysilane, and the mass ratio of isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent to γ-(methacryloyloxy)propyltrimethoxysilane is 1-10:1-10;

[0016] The surface modifier solution is a mixture of the surface modifier and ethanol, and the mass of the surface modifier is 0.8-1.2% of the mass of the composite powder.

[0017] Preferably, the temperature of stirring modification is 100-120°C, the time is 45-60 min, and the stirring rate is 600-800 r / min.

[0018] The present invention also provides a modified composite powder for PVC homogeneous roll floor prepared by the preparation method described above. The whiteness of the modified composite powder for PVC homogeneous roll floor is ≥92%, D50≤6 μm, and the oil absorption value is ≤20 mL / 100 g.

[0019] The present invention also provides the application of the modified composite powder for PVC homogeneous roll floor in building materials and decorative materials.

[0020] The beneficial effects of the present invention include:

[0021] The present invention calcines mica concentrate and wollastonite concentrate at 300-400 °C to reduce organic matter, improve the purity of minerals and the whiteness of the composite powder, and reduce the influence of the composite powder on the hue of the product. The present invention uses a fluidized bed jet mill for grinding and a betaine-type amphoteric dispersant for dispersion, which ensures the layered structure of mica and the acicular structure of wollastonite, improves the elasticity required for the product, and can also ensure the wear resistance, weather resistance, acid and alkali resistance, heat resistance and low shrinkage performance of the product. In addition, the present invention uses isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent (TCA-K44) and γ-(methacryloyloxy)propyltrimethoxysilane (KH-570) to modify the composite powder, which can improve the compatibility of the composite powder with PVC resin and improve the plasticization effect and mechanical properties of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a preparation flow chart of the modified composite powder for the PVC homogeneous roll floor of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0023] The present invention provides a method for preparing a modified composite powder for a PVC homogeneous roll floor, which comprises the following steps:

[0024] 1) The mica concentrate is calcined and then subjected to two-stage jaw crushing in sequence to obtain massive mica;

[0025] The wollastonite concentrate is calcined and then subjected to two-stage jaw crushing in sequence to obtain massive wollastonite;

[0026] 2) The massive mica, massive wollastonite and the polymer dispersant solution are mixed and then ground in a jet mill. The grinding product is subjected to cyclone classification to obtain a composite powder;

[0027] 3) The composite powder is mixed with the surface modifier solution and stirred for modification to obtain a modified composite powder for a PVC homogeneous roll floor.

[0028] In the present invention, before calcination, the mica concentrate and wollastonite concentrate are preferably washed with deionized water and dried in the sun.

[0029] In the present invention, the mass content of mica in the mica concentrate is preferably ≥95%, more preferably ≥96%, and even more preferably ≥97%. The mass content of calcium silicate in the wollastonite concentrate is preferably ≥95%, more preferably ≥96%, and even more preferably ≥97%. The calcination temperature of the mica concentrate and wollastonite concentrate is independently preferably 300-400 °C, more preferably 330-370 °C, and even more preferably 350-360 °C. The calcination time is independently preferably 60-90 min, more preferably 70-80 min, and even more preferably 75 min.

[0030] In the present invention, the mass ratio of blocky muscovite and blocky wollastonite is preferably 1:3-6, further preferably 1:4-5, and more preferably 1:4.5; the mass of the polymer dispersant is preferably 0.3-0.7% of the total mass of the blocky muscovite and blocky wollastonite, further preferably 0.4-0.6%, and more preferably 0.5%; the polymer dispersant is preferably a betaine-type amphoteric dispersant.

[0031] In the present invention, the polymer dispersant solution is preferably obtained by mixing the polymer dispersant with water at 80 to 85° C., and more preferably obtained by mixing the polymer dispersant with water at 82 to 83° C. The mass fraction of the polymer dispersant in the polymer dispersant solution is preferably 6 to 10%, more preferably 7 to 9%, and more preferably 8%. The polymer dispersant is preferably one or more of carboxylic acid betaine, sulfonyl betaine, alkyl betaine and phosphate betaine.

[0032] In the present invention, blocky muscovite and blocky wollastonite are added into a fluidized bed airflow mill for grinding, and during the grinding process, a polymer dispersant solution is slowly added.

[0033] In the present invention, the dispersibility of bulk muscovite and bulk wollastonite is improved by adding a polymer dispersant, thereby facilitating the full play of the mineral powder.

[0034] In the present invention, the air flow mill is preferably a fluidized bed air flow mill; during the grinding process, the feed rate is preferably 1.5-2.5 t / h, more preferably 1.8-2.2 t / h, more preferably 2 t / h, the grinding pressure is preferably 0.6-0.8 MPa, more preferably 0.65-0.75 MPa, more preferably 0.7 MPa, the nozzle diameter is preferably 1-3 mm, more preferably 1.5-2.5 mm, more preferably 2 mm, the air flow velocity is preferably 300-350 m / s, more preferably 310-340 m / s, more preferably 320-325 m / s, the grinding time is preferably 60-75 min, more preferably 65-70 min, more preferably 66-68 min; the speed of the turbine classifier for cyclone classification is preferably 1000-1300 r / min, more preferably 1050-1200 r / min, more preferably 1100-1150 r / min.

[0035] In the present invention, the fluidized bed jet mill integrates multi-nozzle technology, fluidized bed technology and turbine classification technology, realizing the diversification of material flow fields, fluidization of material layers and horizontal classification; the grinding pressure is the pressure difference generated inside the jet mill; and the cyclone classification adopts a cyclone classification system.

[0036] In the present invention, the surface modifier is preferably isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent (TCA-K44) and γ-(methacryloyloxy)propyltrimethoxysilane (KH-570). The mass ratio of isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent to γ-(methacryloyloxy)propyltrimethoxysilane is preferably 1-10:1-10, more preferably 3-7:3-7, and even more preferably 5-6:5-6;

[0037] The surface modifier solution is preferably a mixture of the surface modifier and ethanol. The mass fraction of the surface modifier in the surface modifier solution is preferably 8-12%, more preferably 9-11%, and even more preferably 10%. The mass of the surface modifier is preferably 0.8-1.2% of the mass of the composite powder, more preferably 0.9-1.1%, and even more preferably 1.0%.

[0038] In the present invention, the temperature for stirring modification is preferably 100-120 °C, more preferably 105-115 °C, and even more preferably 108-110 °C. The time is preferably 45-60 min, more preferably 48-55 min, and even more preferably 50-53 min. The stirring rate is preferably 600-800 r / min, more preferably 650-750 r / min, and even more preferably 700 r / min.

[0039] In the present invention, after the composite powder is mixed with the surface modifier solution and subjected to stirring modification, it is preferably depolymerized and dispersed, collected, and packaged in sequence to obtain the modified composite powder for PVC homogeneous coil flooring.

[0040] The present invention also provides the modified composite powder for PVC homogeneous coil flooring prepared by the preparation method described above. The whiteness of the modified composite powder for PVC homogeneous coil flooring is ≥92%, D50 ≤ 6 μm, and the oil absorption value ≤ 20 mL / 100 g.

[0041] In the present invention, the whiteness of the modified composite powder for PVC homogeneous coil flooring is preferably ≥92.5%, more preferably ≥93%. D50 is preferably ≤ 5.8 μm, more preferably ≤ 5.5 μm. The oil absorption value is preferably

[0042] ≤ 19 mL / 100 g, more preferably ≤ 18 mL / 100 g.

[0043] The present invention also provides the application of the modified composite powder for PVC homogeneous coil flooring in building materials and decorative materials.

[0044] In the present invention, the modified composite powder for PVC homogeneous coil flooring has good compatibility with PVC resin, and the wear resistance, weather resistance, heat resistance, and low shrinkage performance of the product are improved. At the same time, the excellent mechanical properties of the product can be ensured.

[0045] The technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0046] Example 1

[0047] Select muscovite concentrate with a muscovite mass content of 95% and wollastonite concentrate with a calcium silicate mass content of 95%. After washing the muscovite concentrate and wollastonite concentrate with deionized water and drying in the sun, they are respectively calcined in a calcination furnace at 300 °C for 60 min. After the calcination is completed, two-stage jaw crushing is carried out to obtain block-shaped muscovite and block-shaped wollastonite (both with sizes of 4 - 6 cm).

[0048] The block-shaped muscovite and block-shaped wollastonite are mixed at a mass ratio of 1:3 and then put into a fluidized bed jet mill for dry grinding. The feeding rate is controlled at 1.5 t / h, the grinding pressure of the jet mill (pressure difference generated inside the jet mill) is 0.6 MPa, the diameter of the air jet nozzle is 1 mm, the air flow (air stream) rate is 300 m / s, and the grinding time is 60 min. During the grinding process, a cetyl dimethyl betaine solution (cetyl dimethyl betaine is mixed evenly with deionized water at 80 °C, and the mass fraction of cetyl dimethyl betaine in the cetyl dimethyl betaine solution is 8%) is added at a rate of 800 mL / h. The mass of cetyl dimethyl betaine is 0.3% of the total mass of the block-shaped muscovite and block-shaped wollastonite. After grinding, it is collected through a cyclone classification system, and after cyclone classification, it is returned to the fluidized bed jet mill for re-grinding. The rotational speed of the turbo classifier is 1000 r / min, and a composite powder is collected.

[0049] The composite powder is then put into a high-speed mixer, and a mixed solution of a surface modifier and absolute ethanol (the mass fraction of the surface modifier in the mixed solution is 10%) is added. The mass of the surface modifier is 0.8% of the mass of the composite powder. The surface modifier is TCA-K44 and KH-570 with a mass ratio of 1:1; modification is carried out at 100 °C and a stirring rate of 600 r / min for 45 min. After the modification is completed, it is depolymerized, dispersed, collected, and packaged to obtain a modified composite powder for PVC homogeneous sheet flooring.

[0050] Example 2

[0051] Select muscovite concentrate with a muscovite mass content of 96% and wollastonite concentrate with a calcium silicate mass content of 96%. After washing the muscovite concentrate and wollastonite concentrate with deionized water and drying in the sun, they are respectively calcined in a calcination furnace at 330 °C for 70 min. After the calcination is completed, two-stage jaw crushing is carried out to obtain block-shaped muscovite and block-shaped wollastonite (both with sizes of 4 - 6 cm).

[0052] Block mica and block wollastonite are mixed at a mass ratio of 1:4 and then fed into a fluidized bed jet mill for dry grinding. The feeding rate is controlled at 1.8 t / h, the grinding pressure of the jet mill (pressure difference generated inside the jet mill) is 0.65 MPa, the diameter of the air jet nozzle is 1.5 mm, the air flow (air stream) rate is 315 m / s, and the grinding time is 65 min. During the grinding process, a dodecyl hydroxypropyl sulfobetaine solution (dodecyl hydroxypropyl sulfobetaine is mixed evenly with deionized water at 80 °C, and the mass fraction of dodecyl hydroxypropyl sulfobetaine in the dodecyl hydroxypropyl sulfobetaine solution is 8%) is added at a rate of 800 mL / h. The mass of dodecyl hydroxypropyl sulfobetaine is 0.4% of the total mass of block mica and block wollastonite. After grinding, it is collected through a cyclone classification system, and after cyclone classification, it is returned to the fluidized bed jet mill for re-grinding. The rotational speed of the turbine classifier is 1050 r / min, and a composite powder is collected.

[0053] The composite powder is then fed into a high-speed mixer, and a mixed solution of a surface modifier and absolute ethanol (the mass fraction of the surface modifier in the mixed solution is 9%) is added. The mass of the surface modifier is 0.9% of the mass of the composite powder. The surface modifier is TCA-K44 and KH-570 with a mass ratio of 1:1. It is modified under the conditions of 105 °C and a stirring rate of 650 r / min for 50 min. After the modification is completed, it is further depolymerized, dispersed, collected, and packaged to obtain a modified composite powder for PVC homogeneous sheet flooring.

[0054] Example 3

[0055] Mica concentrate with a mica mass content of 96% and wollastonite concentrate with a calcium silicate mass content of 96% are selected. After the mica concentrate and wollastonite concentrate are washed with deionized water and dried in the sun, they are respectively calcined in a calcination furnace at 350 °C for 75 min. After the calcination is completed, two-stage jaw crushing is carried out to obtain block mica and block wollastonite (both with sizes of 4 - 6 cm).

[0056] Mix massive muscovite and massive wollastonite in a mass ratio of 1:4.5, then put them into a fluidized bed jet mill for dry grinding. Control the feeding rate at 2 t / h, the grinding pressure of the jet mill (the pressure difference generated inside the jet mill) at 0.7 MPa, the diameter of the air jet nozzle at 2 mm, the air flow (air current) rate at 320 m / s, and the grinding time at 68 min. During the grinding process, add a tetradecyl phosphate betaine solution (tetradecyl phosphate betaine is mixed evenly with deionized water at 80 °C, and the mass fraction of tetradecyl phosphate betaine in the tetradecyl phosphate betaine solution is 9%) at a rate of 800 mL / h. The mass of tetradecyl phosphate betaine is 0.5% of the total mass of massive muscovite and massive wollastonite. After grinding, collect through a cyclone classification system. After cyclone classification, return to the fluidized bed jet mill for re-grinding. The rotational speed of the turbo classifier is 1100 r / min, and a composite powder is collected.

[0057] Put the composite powder into a high-speed mixer, and add a mixed solution of a surface modifier and absolute ethanol (the mass fraction of the surface modifier in the mixed solution is 10%). The mass of the surface modifier is 1.0% of the mass of the composite powder. The surface modifier is TCA-K44 and KH-570 with a mass ratio of 1:1. Modify under the conditions of 110 °C and a stirring rate of 700 r / min for 53 min. After modification, carry out depolymerization and dispersion, collection and packaging to obtain a modified composite powder for PVC homogeneous roll floor.

[0058] Comparative Example 1

[0059] Commercially available mica powder, manufacturer: Chuzhou Kaijin Sericite Co., Ltd.; model: KG-5.

[0060] Comparative Example 2

[0061] Commercially available wollastonite powder, manufacturer: Jiangxi Aote Technology Co., Ltd.; model: wollastonite mineral fiber for rubber and plastics.

[0062] Carry out relevant index detections on the modified composite powder for PVC homogeneous roll floor prepared in Examples 1 to 3, the commercially available mica powder in Comparative Example 1, and the commercially available wollastonite powder in Comparative Example 2 according to HG / T 3249.2-2013. The detection results of various performance indexes are shown in Table 1.

[0063] Table 1 Detection results of powders in Examples and Comparative Examples

[0064]

[0065]

[0066] Application Example 1

[0067] The modified composite powder prepared in Examples 1 to 3, the commercially available mica powder in Comparative Example 1, and the commercially available wollastonite powder in Comparative Example 2 were respectively applied to PVC homogeneous coil floors for performance testing. The specific method was as follows: 100 g of commercially available PVC (SG-5) resin, 50 g of filler (the modified composite powder in the example, the commercially available mica powder or commercially available wollastonite powder in the comparative example), 30 g of DOTP, 5.5 g of calcium-zinc stabilizer, 0.6 g of PE wax, and 6 g of CPE were mixed evenly, and then extrusion molding was carried out. The parameters of extrusion molding were: the temperature of the feeding section was 160 °C, the temperature of the melting section was 170 °C, the temperature of the homogenization section was 180 °C, the temperature of the die head was 190 °C, and the screw speed was 30 r / min. The finished products (width 1500 mm, thickness 3 mm) were tested and evaluated according to the requirements of GB / T 11982.2-2015 Polyvinyl chloride coil floors - Part 2: Homogeneous polyvinyl chloride coil floors. The results are shown in Table 2.

[0068] Table 2 Performance test results of PVC homogeneous coil floors prepared in examples and comparative examples

[0069] Detection index Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Wear resistance level T level T level T level M level P level Stain resistance level Level 1 Level 1 Level 1 Level 3 Level 3 Heating warpage 2mm 2mm 2mm 8mm 4mm Color difference Not obvious Not obvious Not obvious Obvious Obvious Defect / crack None None None Small crack Small crack Flexibility No cracking No cracking No cracking Cracking Cracking

[0070] As can be seen from Table 2, the PVC homogeneous coil floors prepared from the modified composite powder of the present invention and PVC can meet the requirements in all the test indexes of the finished products, and the effect is better than that of simply using one kind of mica powder or one kind of wollastonite powder.

[0071] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a modified composite powder for PVC homogeneous coiled floor, characterized in that: The following steps are included: 1) The muscovite concentrate is calcined and crushed in two stages to obtain blocky muscovite; The wollastonite concentrate is calcined and crushed in two stages to obtain blocky wollastonite; 2) mixing the blocky muscovite, the blocky wollastonite and the polymer dispersant solution and grinding them in a jet mill, and subjecting the ground product to cyclone classification to obtain a composite powder; 3) The composite powder is mixed with a surface modifier solution, and stirred for modification to obtain a modified composite powder for PVC homogeneous coiled flooring.

2. The preparation method according to claim 1, characterized in that: The mass content of muscovite in the muscovite concentrate is ≥95%, the mass content of calcium silicate in the wollastonite concentrate is ≥95%, the calcination temperature of the muscovite concentrate and the wollastonite concentrate is independently 300-400°C, and the calcination time is independently 60-90 minutes.

3. The preparation method according to claim 1 or 2, characterized in that: The mass ratio of massive muscovite to massive wollastonite is 1:3-6; the mass of the polymer dispersant is 0.3-0.7% of the total mass of the massive muscovite and the massive wollastonite; the polymer dispersant is a betaine type amphoteric dispersant.

4. The preparation method according to claim 3, characterized in that: The polymer dispersant solution is obtained by mixing the polymer dispersant with water at 80-85° C. The polymer dispersant is one or more of carboxylic acid betaine, sulfo betaine, alkyl betaine and phosphate betaine.

5. The preparation method according to claim 3, characterized in that: The air flow mill is a fluidized bed air flow mill; during the grinding process, the feed rate is 1.5-2.5 t / h, the grinding pressure is 0.6-0.8 MPa, the nozzle diameter is 1-3 mm, the air flow velocity is 300-350 m / s, and the grinding time is 60-75 min; the speed of the turbine classifier of the cyclone classification is 1000-1300 r / min.

6. The preparation method according to claim 1 or 5, characterized in that: The surface modifier is an isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent and γ-(methacryloyloxy) propyl trimethoxy silane, and the mass ratio of the isopropoxy tris(ethylenediamino-N-ethoxy) titanate coupling agent to the γ-(methacryloyloxy) propyl trimethoxy silane is 1-10:1-10; The surface modifier solution is a mixed solution of the surface modifier and ethanol, and the mass of the surface modifier is 0.8-1.2% of the mass of the composite powder.

7. The preparation method according to claim 6, characterized in that: The stirring modification temperature is 100-120°C, the time is 45-60min, and the stirring speed is 600-800r / min.

8. The modified composite powder for PVC homogeneous coiled flooring prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The whiteness of the modified composite powder for PVC homogeneous coil flooring is ≥92%, D50 ≤6μm, and the oil absorption value ≤20mL / 100g.

9. Use of the modified composite powder for PVC homogeneous coil flooring according to claim 8 in building materials and decorative materials.

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