WO2022151961A1

WO2022151961A1 - Basalt fiber-reinforced pvc marble tailings composite material and preparation method therefor

Info

Publication number: WO2022151961A1
Application number: PCT/CN2021/141428
Authority: WO
Inventors: 张以河; 张娜; 邸祥云; 张有鹏; 丁冲; 张帅; 孙锋; 苗伟; 马健
Original assignee: 中国地质大学（北京）
Priority date: 2021-01-12
Filing date: 2021-12-27
Publication date: 2022-07-21
Also published as: CN112708227B; CN112708227A

Abstract

The present invention relates to a basalt fiber-reinforced PVC marble tailings composite material and a preparation method therefor. The composite material comprises a main material, a heat stabilizer, a plasticizer, a lubricant, and an additive. The main material comprises a PVC resin, marble tailings, and basalt fibers. The composite material also comprises antibacterial modified polypropylene fibers and a regulator. The antibacterial modified polypropylene fibers are made by blending and spinning marble tailings and polypropylene. The mass fractions of the raw materials in the composite material are as follows: 100 parts of PVC resin, 10-100 parts of marble tailings, 2-12 parts of basalt fibers, 2-8 parts of a heat stabilizer, 1-5 parts of a plasticizer, 0.1-1.2 parts of a lubricant, 0.1-13 parts of an additive, 5-20 parts of antibacterial modified polypropylene fibers, and 5-10 parts of a regulator; the antibacterial modified polypropylene fibers comprise 0.3-4 parts of marble tailings, the remainder being polypropylene fibers.

Description

A kind of basalt fiber reinforced PVC marble tailings composite material and preparation method

technical field

The invention belongs to the technical field of PVC composite materials, in particular to a basalt fiber-reinforced PVC marble tailings composite material and a preparation method.

Background technique

With the continuous consumption of petroleum resources, traditional pure polymer materials begin to develop towards filling inorganic mineral powders. The use of inorganic mineral powders as fillers can effectively reduce the consumption of polymer materials, thereby saving the consumption of petroleum energy. At the same time, the addition of fillers can effectively enhance the mechanical properties of polymer composites and reduce the cost of composites, which has broad research prospects.

Marble tailings are tailings discarded in the process of mining and sorting natural marble. The composition of tailings is still mainly calcite (calcium carbonate), and there are metal and non-metal oxides that are difficult to separate, so it is difficult to be used as marble in industry. During the mining process of marble mines, the tailings production rate is as high as 50%. As the second largest marble-producing country in the world, my country will produce millions of tons of marble tailings every year, but the utilization rate of marble tailings is still less than 10%. Tailings are usually piled up by building open-air tailings ponds, which occupy a lot of land and also cause air and water pollution, endangering the economic property and health of nearby people. Therefore, the utilization of tailings resources is imminent.

At present, most of PVC composite materials use calcium carbonate powder as the main filler for filling composite materials. The cost is high, and the filler material and performance are single, which has limitations in improving the comprehensive performance of PVC composite materials. The invention makes improvements in view of the shortcomings of poor toughness and impact resistance of the indoor PVC composite material.

SUMMARY OF THE INVENTION

In view of the above problems, the present invention provides a basalt fiber-reinforced PVC marble tailings composite material and a preparation method. The composite material includes a main material, a heat stabilizer, a plasticizer, a lubricant and an auxiliary agent, and the main material includes PVC resin, marble tailings and basalt fiber.

The composite material of the present invention adds marble tailings and basalt fiber as the main materials in the PVC resin. Marble tailings are difficult to separate due to their non-metal and metal oxides, and their irregular shapes and sizes are difficult to use as marble. However, because the content of calcium carbonate in marble tailings is as high as 89%, the inventors recycled the marble tailings. , as the main inorganic filler of the composite material, it can effectively replace the existing filler calcium carbonate and play the role of strengthening the PVC composite material. At the same time, various metal and non-metal oxides contained in marble tailings can further improve the strength and hardness of PVC composites. The invention creatively adds basalt fiber to the main material, which can significantly enhance the bending and impact strength of the composite material and improve its toughness.

Preferably, the composite material further includes antibacterial modified polypropylene fibers, and the antibacterial modified polypropylene fibers are obtained by blending marble tailings and polypropylene.

The invention utilizes the characteristics that marble tailings in the raw material contain various metal and non-metal oxides, and utilizes its natural bactericidal effect to blend and spin with polypropylene to obtain antibacterial modified polypropylene fibers, and the antibacterial modified polypropylene fibers are obtained. The propylene fibers are mixed into the composite material, so that the interior decoration or decoration product made from the composite material has high antibacterial properties, antifouling properties and impact strength at the same time, which is suitable for providing a cleaner and safer indoor environment . The reason why marble tailings are not directly used as antibacterial agents in the present invention is because marble tailings, as inorganic materials, have less than ideal compatibility with PVC materials and other raw material reagents, and this characteristic does not affect the use of marble tailings as an inorganic material. The filler increases the strength of the composite material, but to have a good antibacterial effect, it is required that the marble tailings can better enter the composite material. Therefore, the inventors thought of using polypropylene fibers as the carrier of marble tailings, first blending them to obtain the antibacterial modified polypropylene fibers, and then adding the antibacterial modified polypropylene fibers to the composite material, Materials with better antibacterial properties can be obtained.

Optionally, the particle size of the marble tailings in the main material is 8-10 μm, and the basalt fiber is 5-10 mm, which is helpful for better mixing with PVC resin and other reagents.

Optionally, the thermal stabilizer is selected from a calcium-zinc composite stabilizer, a lead-based composite stabilizer, an organic tin-based stabilizer or a barium-zinc composite stabilizer.

Optionally, the plasticizer is selected from one or both of dioctyl phthalate and epoxidized soybean oil.

Optionally, the lubricant is selected from one or both of stearic acid or polyethylene wax.

Optionally, the auxiliary agent is selected from one or both of oxidized polyethylene and chlorinated polyethylene.

Optionally, the composite material further includes a conditioning agent, and the conditioning agent is paraffin.

Optionally, the particle size of the marble tailings in the antibacterial modified polypropylene fiber is 0.1-0.6 μm, and the length of the antibacterial modified polypropylene fiber is 3-7 mm. Polypropylene fiber has the characteristics of impact resistance, corrosion resistance and wear resistance, low density/light weight, hydrophobicity, and insulation and heat preservation. Adding polypropylene fiber as a filler to the composite material can improve the performance of the composite material by using less polypropylene fiber. impact resistance of the composites.

Optionally, the mass fraction of raw materials in the composite material is as follows: 100 parts of PVC resin, 10-100 parts of marble tailings, 2-12 parts of basalt fiber, 2-8 parts of heat stabilizer, and 1-5 parts of plasticizer , 0.1-1.2 parts of lubricant, 0.1-13 parts of auxiliary agent, 5-20 parts of antibacterial modified polypropylene fiber, and 5-10 parts of conditioner. The marble tailings in the antibacterial modified polypropylene fibers are 0.3-4 parts, and the rest are polypropylene fibers.

Preferably, 40-100 parts of the marble tailings, 6-12 parts of basalt fibers, 5-10 parts of antibacterial modified polypropylene fibers, and 0.3-2 parts of marble tailings in the antibacterial modified polypropylene fibers.

The present invention also provides a preparation method of the basalt fiber-reinforced PVC marble tailings composite material, and the preparation method comprises the following steps:

(1) Use jet mill to grind marble tailings to 8-10μm, then dry in oven; cut basalt fiber to 5-10mm;

(2) mixing the heat stabilizer, plasticizer, lubricant, auxiliary agent and regulator in a high-speed mixer at a temperature of 30-60° C. to obtain an additive mixture;

(3) mixing PVC resin, marble tailings and basalt fiber obtained in step (1) with the additive mixture in a high-speed mixer, then in a low-speed mixer to obtain a mixture;

(4) the mixture obtained in step (3) is processed in an open mill for 4-8min, and the processing temperature is 165-170 ° C;

(5) vulcanizing the open-smelting sample prepared in step (4) in a flat vulcanizer for 5-8min, the vulcanization temperature is 165-175°C, and the pressure is 8-10MPa;

(6) The vulcanized sample prepared in step (5) is allowed to stand at room temperature for 12-24 hours for stress release.

Optionally, the above step (3) is specifically as follows: (a) mixing the PVC resin with the additive mixture obtained in step (2) of 1/3 mass in a high-speed mixer, at a temperature of 30-90 ° C, to obtain the first Raw material mixture; (b) mixing the marble tailings and basalt fibers obtained in step (1) and the additive mixture obtained in step (2) of 2/3 mass in a high-speed mixer, at a temperature of 30-90 ° C, to obtain the first Two raw material mixtures; (c) mixing the first raw material mixture and the second raw material mixture in a high-speed mixer for 20-40min, at a temperature of 70-90°C; then in a low-speed mixer for 20-30min at a temperature of 70°C -90°C to obtain a mixture.

Optionally, the preparation method of the antibacterial modified polypropylene fiber comprises the following steps:

(7) The marble tailings are milled to 0.1-0.6 μm by jet mill, and then dried in an oven;

(8) the marble tailings obtained in step (7) are vacuum-deposited on the surface of the slice, and then blended with ordinary polypropylene slices to obtain antibacterial modified polypropylene fibers;

(9) The antibacterial modified polypropylene fiber is processed into a length of 3-7mm.

Optionally, the antibacterial modified polypropylene fiber is added to the step (c), and is mixed together with the first raw material mixture and the second raw material mixture in a high-speed mixer for 20-40 minutes at a temperature of 70-90° C.; then Mix the materials in a low-speed mixer for 20-30 minutes at a temperature of 70-90° C. to obtain a mixed material.

The basalt fiber-reinforced PVC marble tailings composite material and the preparation method of the present invention have the following beneficial effects: (1) the present invention uses marble tailings to replace the traditional calcium carbonate filler, aiming to ensure the performance requirements of the composite material Resource utilization of tailings is realized under the circumstance of the present invention; (2) the marble tailings used in the present invention are a kind of large-scale solid waste that urgently needs to be treated, and as fillers, marble tailings fillers are easy to obtain and save a lot of cost; (3) The present invention uses basalt fiber to strengthen the PVC/marble tailings composite material, which can effectively improve the toughness of the composite material and greatly improve the overall mechanical properties of the composite material; (4) the present invention utilizes antibacterial modified polypropylene fibers to make the composite material prepared. The interior decoration or decoration products have high antibacterial, antifouling and impact strength at the same time, suitable for providing a cleaner and safer indoor environment.

Detailed ways

Example 1

The basalt fiber-reinforced PVC marble tailings composite material described in this example has the following mass fractions of raw materials: 100 parts of PVC resin, 40 parts of marble tailings (10 μm), 6 parts of basalt fiber (10 mm), calcium-zinc composite stabilizer 5 parts, 1.5 parts of epoxidized soybean oil, 0.2 part of stearic acid, 0.2 part of polyethylene wax, 0.4 part of oxidized polyethylene, 6 parts of chlorinated polyethylene, and 5 parts of paraffin wax; the preparation method is as follows:

(1) Use jet mill to grind marble tailings to 10μm, then dry in oven; cut basalt fiber to 10mm;

(2) mixing calcium-zinc composite stabilizer, epoxidized soybean oil, stearic acid, polyethylene wax, oxidized polyethylene, chlorinated polyethylene and paraffin in a high-speed mixer at a temperature of 60° C. to obtain an additive mixture;

(3) mixing PVC resin, marble tailings and basalt fiber obtained in step (1) and the additive mixture in a high-speed mixer, at a temperature of 90° C., and then in a low-speed mixer for 20min, at a temperature of 70° C. ℃ to obtain a mixture;

(4) the mixture obtained in step (3) is processed in an open mill for 4min, and the processing temperature is 165 ° C;

(5) vulcanizing the open-smelting sample prepared in step (4) in a flat-plate vulcanizer for 5min, the vulcanization temperature is 165°C, and the pressure is 10MPa;

(6) The vulcanized sample prepared in step (5) was allowed to stand at room temperature for 24 hours for stress release.

Example 2

The basalt fiber-reinforced PVC marble tailings composite material described in this example has the same mass fraction of raw materials as in Example 1.

The step (3) in the preparation method is: (a) mixing the PVC resin with the additive mixture obtained in the step (2) of 1/3 mass in a high-speed mixer at a temperature of 90° C. to obtain a first raw material mixture; ( b) mixing the marble tailings and basalt fibers obtained in step (1) with the additive mixture obtained in step (2) of 2/3 mass in a high-speed mixer at a temperature of 90° C. to obtain a second raw material mixture; (c) ) Mixing the first raw material mixture and the second raw material mixture in a high-speed mixer for 20min at a temperature of 90°C; then in a low-speed mixer for 20min at a temperature of 70°C to obtain a mixture.

Other preparation steps are the same as in Example 1.

Example 3

The basalt fiber-reinforced PVC marble tailings composite material described in this example has the following mass fractions of raw materials: 100 parts of PVC resin, 40 parts of marble tailings (10 μm), 6 parts of basalt fiber (5 mm), calcium-zinc composite stabilizer 5 parts, 1.5 parts of epoxidized soybean oil, 0.2 parts of stearic acid, 0.2 parts of polyethylene wax, 0.4 parts of oxidized polyethylene, 6 parts of chlorinated polyethylene, 5 parts of paraffin, 5 parts of antibacterial modified polypropylene fiber (7mm) , of which 0.3 parts (0.1 μm) of marble tailings and 4.7 parts of polypropylene fibers; the preparation method is as follows:

(3) mixing the PVC resin with the additive mixture obtained in step (2) of 1/3 mass in a high-speed mixer at a temperature of 90° C. to obtain the first raw material mixture;

(4) the marble tailings and basalt fiber obtained in step (1) and the additive mixture obtained in step (2) of 2/3 quality are mixed in a high-speed mixer, and the temperature is 90 ° C to obtain the second raw material mixture;

(5) The marble tailings are milled to 0.1 μm by jet mill, and then dried in an oven;

(6) the marble tailings obtained in step (5) are vacuum-deposited on the surface of the slice, and then blended with ordinary polypropylene slices to obtain antibacterial modified polypropylene fibers; the antibacterial modified polypropylene fibers are processed into a length of 3 mm;

(7) mixing the antibacterial modified polypropylene fibers, the first raw material mixture and the second raw material mixture in a high-speed mixer for 20 min at a temperature of 90°C; then in a low-speed mixer for 20min at a temperature of 70°C to obtain Mixture;

(8) the mixture obtained in step (7) is processed in an open mill for 4min, and the processing temperature is 165 ° C;

(9) vulcanizing the open-smelting sample prepared in step (8) in a flat vulcanizer for 5 minutes, the vulcanization temperature is 165°C, and the pressure is 10MPa;

(10) The vulcanized sample prepared in step (9) was allowed to stand at room temperature for 24 hours for stress release.

Example 4

In the basalt fiber-reinforced PVC marble tailings composite material described in this example, the particle size of marble tailings in the main material is 8 μm, and the basalt fiber is 10 mm. Other raw materials and preparation methods are the same as those in Example 3.

Example 5

In the basalt fiber-reinforced PVC marble tailings composite material described in this example, the particle size of the marble tailings in the antibacterial modified polypropylene fibers in the raw materials is 0.6 μm, and the antibacterial modified polypropylene fibers are 3 mm. Other raw materials and preparations The method is the same as in Example 3.

Example 6

In the basalt fiber-reinforced PVC marble tailings composite material described in this example, the mass of marble tailings in the main material is 100 parts, and the mass of basalt fiber is 12 parts. Other raw materials and preparation methods are the same as in Example 3.

Example 7

In the basalt fiber-reinforced PVC marble tailings composite material described in this example, the mass parts of the antibacterial modified polypropylene fibers in the raw material are 2 parts by mass of the marble tailings, the antibacterial modified polypropylene fibers are 10 parts, and the polypropylene fiber is 10 parts by mass. Fiber is 8 parts, and other raw materials and preparation methods are the same as in Example 3.

Example 8

In the basalt fiber-reinforced PVC marble tailings composite material described in this example, the mass parts of marble tailings in the main material are 10 parts, and the mass parts of basalt fibers are 2 parts. Other raw materials and preparation methods are the same as those in Example 3.

Example 9

In the basalt fiber-reinforced PVC marble tailings composite material described in this example, the mass parts of the marble tailings in the antibacterial modified polypropylene fibers in the raw materials are 4 parts, the antibacterial modified polypropylene fibers are 20 parts, and the polypropylene fibers are 20 parts by mass. Fiber is 16 parts, and other raw materials and preparation methods are the same as in Example 3.

Example 10

The basalt fiber-reinforced PVC marble tailings composite material described in this embodiment has the following mass fractions of raw materials: 100 parts of PVC resin, 100 parts of marble tailings (8 μm), 12 parts of basalt fiber (5 mm), calcium-zinc composite stabilizer 8 parts, 5 parts epoxidized soybean oil, 6 parts stearic acid, 6 parts polyethylene wax, 7 parts oxidized polyethylene, 6 parts chlorinated polyethylene, 10 parts paraffin wax, 10 parts antibacterial modified polypropylene fiber (3mm) , including 2 parts of marble tailings (0.1 μm) and 8 parts of polypropylene fibers. The preparation method is the same as that of Example 3.

Example 11

The basalt fiber-reinforced PVC marble tailings composite material described in this example contains 2 parts of calcium-zinc composite stabilizer, 1 part of epoxy soybean oil, 0.1 part of stearic acid, 0.1 part of oxidized polyethylene, other raw materials and preparation methods are the same as Example 10 is the same.

Comparative Example 1

The basalt fiber-reinforced PVC marble tailings composite material described in this comparative example does not contain marble tailings and antibacterial modified polypropylene fibers.

Comparative Example 2

The basalt fiber reinforced PVC marble tailings composite material described in this comparative example does not contain basalt fiber and antibacterial modified polypropylene fiber.

Comparative Example 3

The basalt fiber-reinforced PVC marble tailings composite material described in this comparative example does not contain marble tailings, basalt fibers and antibacterial modified polypropylene fibers.

Table 1 Effect comparison of embodiment 1-11 and comparative example 1-3

It can be seen from the above table that the composite material provided by the present invention has good strength and toughness. Specifically, since Example 2 adopts the preparation method of step-by-step mixing, compared with Example 1, the strength and The toughness is good; compared with Example 2, Example 3 added the antibacterial modified polypropylene fiber, the toughness is better, and the antibacterial performance is greatly improved.

Compared with Example 3, in the main material of Example 4, the granularity of marble tailings is finer, the basalt fiber is longer, and its strength and toughness are slightly better; compared with Example 3, the antibacterial modified polypropylene fiber of Example 5 is The granularity of the medium marble tailings is slightly larger, the antibacterial modified polypropylene fiber is shorter, and its toughness and antibacterial properties are slightly worse; The toughness and strength are relatively large, and the amount of the antibacterial modified polypropylene fiber of Example 7 and the marble tailings therein is relatively large, its toughness is better, and the antibacterial performance is improved greatly; the marble tailings and basalt in the main materials of Example 8 are large. The fiber dosage is less, and its strength and toughness are poor; the antibacterial modified polypropylene fiber of Example 9 and the marble tailings therein are further increased, but its toughness and antibacterial properties are limited; Example 10 combines the above discussions The experimental factors were better in toughness, strength and antibacterial performance; Example 11 had less additive dosage, and the effect was poor.

Compared with Example 1, Comparative Example 1 does not contain marble tailings and antibacterial modified polypropylene fibers, and its strength decreases to some extent, and Comparative Example 2 does not contain basalt fibers and antibacterial modified polypropylene fibers, and its toughness decreases to some extent , Comparative Example 3 does not contain marble tailings, basalt fiber and antibacterial modified polypropylene fiber, and its toughness and strength have decreased.

To sum up, the basalt fiber reinforced PVC marble tailings composite material and preparation method provided by the present invention utilize marble tailings, basalt fiber and antibacterial modified polypropylene fiber to synergistically enhance the toughness, strength and stability of the composite material. It has antibacterial properties, good effect and low cost, is suitable for interior building decoration materials, and has good industrial application prospects.

Claims

A basalt fiber-reinforced PVC marble tailings composite material, characterized in that the composite material includes main materials, heat stabilizers, plasticizers, lubricants and additives, and the main materials include PVC resin, marble tailings and basalt fibers.
The composite material according to claim 1, characterized in that, the composite material further comprises antibacterial modified polypropylene fibers, and the antibacterial modified polypropylene fibers are obtained by blending marble tailings and polypropylene.
The composite material according to claim 2, wherein the particle size of the marble tailings in the antibacterial modified polypropylene fibers is 0.1-0.6 μm, and the length of the antibacterial modified polypropylene fibers is 3-7 mm.
The composite material according to claim 1, wherein the marble tailings in the main material have a particle size of 8-10 μm, and the basalt fiber is 5-10 mm.
The composite material according to claim 1, wherein the thermal stabilizer is selected from calcium-zinc composite stabilizer, lead-based composite stabilizer, organic tin-based stabilizer or barium-zinc composite stabilizer;

The plasticizer is selected from one or both of dioctyl phthalate or epoxidized soybean oil;

Described lubricant is selected from one or both in stearic acid or polyethylene wax;

The auxiliary agent is selected from one or both of oxidized polyethylene and chlorinated polyethylene.
The composite material according to claim 2, characterized in that, the composite material further comprises a conditioning agent, and the conditioning agent is paraffin.
The composite material according to claim 6, wherein the mass fraction of the raw materials in the composite material is as follows: 100 parts of PVC resin, 10-100 parts of marble tailings, 2-12 parts of basalt fiber, 2-12 parts of heat stabilizer 8 parts, 1-5 parts of plasticizer, 0.1-1.2 parts of lubricant, 0.1-13 parts of auxiliary, 5-20 parts of antibacterial modified polypropylene fiber, 5-10 parts of conditioner; the antibacterial modified polypropylene The marble tailings in the fiber are 0.3-4 parts, and the rest are polypropylene fibers.
A preparation method of the composite material described in any one of claims 1-7, comprising the following steps:

(1) Use jet mill to grind marble tailings to 8-10μm, then dry in oven; cut basalt fiber to 5-10mm;

(2) mixing the heat stabilizer, plasticizer, lubricant, auxiliary agent and regulator in a high-speed mixer at a temperature of 30-60° C. to obtain an additive mixture;

(3) the marble tailings and basalt fiber obtained by PVC resin, step (1) and the additive mixture are mixed in a high-speed mixer, then mixed in a low-speed mixer to obtain a mixture;

(4) the mixture obtained in step (3) is processed in an open mill for 4-8min, and the processing temperature is 165-170 ° C;

(5) vulcanizing the open-smelting sample prepared in step (4) in a flat vulcanizer for 5-8min, the vulcanization temperature is 165-175°C, and the pressure is 8-10MPa;

(6) The vulcanized sample prepared in step (5) is allowed to stand at room temperature for 12-24 hours for stress release.
The preparation method according to claim 8, wherein the step (3) is specifically: (a) mixing the PVC resin with the additive mixture obtained in the step (2) of 1/3 mass in a high-speed mixer material, the temperature is 30-90 ℃, and the first raw material mixture is obtained; (b) the marble tailings and basalt fibers obtained in step (1) and the additive mixture obtained in step (2) of 2/3 mass are placed in a high-speed mixer. Mixing materials at a temperature of 30-90 °C to obtain a second raw material mixture; (c) mixing the first raw material mixture and the second raw material mixture in a high-speed mixer for 20-40 min, at a temperature of 70-90 °C; then mixing at a low speed Mix the material in the feeder for 20-30min and the temperature is 70-90℃ to obtain the mixed material.
The preparation method according to claim 9, wherein the preparation method of the antibacterial modified polypropylene fiber comprises the following steps:

(7) The marble tailings are milled to 0.1-0.6 μm by jet mill, and then dried in an oven;

(8) the marble tailings obtained in step (7) are vacuum-deposited on the surface of the slice, and then blended with ordinary polypropylene slices to obtain antibacterial modified polypropylene fibers;

(9) processing the antibacterial modified polypropylene fiber into a length of 3-7mm;

The antibacterial modified polypropylene fiber is added to the step (c), and is mixed together with the first raw material mixture and the second raw material mixture in a high-speed mixer for 20-40 minutes at a temperature of 70-90° C.; and then mixed at a low speed Mixing in the machine for 20-30min, temperature 70-90℃, to obtain the mixture.