Preparation method of long-acting wear-resistant PVC (polyvinyl chloride) non-slip mat

Abstract

The invention discloses a preparation method of a long-acting wear-resistant PVC (polyvinyl chloride) non-slip mat, and belongs to the field of high polymer material processing. The method comprises three steps of raw material pretreatment, mixing and modification, and compression molding. According to the invention, plant powder, glass fiber and other reinforcing fillers are introduced, and a silane coupling agent and a compatilizer are adopted for interface modification, so that the compatibility and interface bonding force of the fillers and a PVC matrix are improved, and the PVC non-slip mat with excellent wear resistance for a long time is prepared by optimizing molding process conditions. The method is easy and convenient to operate, environmentally friendly and suitable for large-scale industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polymer material processing, and particularly relates to a preparation method of long-acting wear-resistant PVC anti-slip mat. BACKGROUND

[0002] PVC (polyvinyl chloride) anti-slip mat is a kind of floor laying material widely used in bathroom, kitchen, swimming pool and other slippery environment, which is popular in the market due to its good anti-slip property, easy cleaning and economy. However, the actual service life of the existing PVC anti-slip mat is often limited by the wear resistance, especially in high-frequency and high-load use scenarios, the surface is easy to wear, which affects the anti-slip effect and appearance aesthetics of the product, and it is difficult to meet the demand of consumers for long-acting wear-resistant performance.

[0003] In order to improve the wear resistance of PVC anti-slip mat, the industry often adopts the way of introducing fillers or reinforcing agents into the PVC matrix, such as rice husk powder, glass fiber, talc powder, etc. These fillers not only can reduce the cost, but also can improve the mechanical properties of the material to a certain extent. For example, patent ZL 201710254441.8 relates to a PVC modified material for anti-slip carpet and a preparation method thereof, which comprises the following raw materials by weight: PVC resin 80-120 parts, plasticizer 40-60 parts, heavy calcium carbonate 10-15 parts, light calcium carbonate 5-15 parts, high composite stabilizer 3-7 parts, chlorinated polyethylene 1-3 parts, wear-resistant modifier 1-3 parts, anti-slip agent 0.3-0.7 parts, anti-ultraviolet agent 0.6-1.0 parts, antioxidant 0.3-0.7 parts, lubricant 0.3-0.7 parts.

[0004] However, the bonding force between the traditional fillers and the PVC matrix is weak, which is easy to cause delamination or falling off in the material due to stress concentration during use, thereby affecting the overall performance of the product. In addition, due to the poor dispersibility of the fillers in the PVC matrix, agglomeration phenomenon is easy to occur between the filler particles, which not only reduces the reinforcing effect, but also may cause uneven surface or defects of the product.

[0005] In summary, the production method of traditional PVC anti-slip mat has certain limitations in improving wear resistance and prolonging service life. SUMMARY

[0006] In order to overcome at least one technical problem in the above background art, the present method proposes a preparation method of long-acting wear-resistant PVC anti-slip mat, and develops a preparation method of long-acting wear-resistant anti-slip mat combining plant powder, inorganic fillers such as glass fiber and PVC matrix, especially combining filler surface modification technology and optimizing mold forming process, which is the key to improve the performance of the product.

[0007] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0008] A preparation method of a long-acting wear-resistant PVC non-slip mat, comprising the following steps:

[0009] (1) Raw material pretreatment: 15 to 30 parts by weight of plant powder, 50 to 75 parts of PVC, 10 to 20 parts of glass fiber, 1 to 5 parts of inorganic filler, 1 to 3 parts of heat stabilizer, 1 to 3 parts of antioxidant and 1 to 3 parts of plasticizer are weighed, and the raw materials are placed in an oven at 80 to 90℃ for drying for 10 to 15 hours;

[0010] (2) Mixing and modification: 5 to 10 parts of anhydrous ethanol and 1 to 3 parts of silane coupling agent, 1 to 3 parts of compatibilizer are added to the dried raw materials, and stirred by high-speed stirring equipment at 1500 to 2000 revolutions per minute for 10 to 20 minutes to ensure that the silane coupling agent is evenly coated on the surface of the plant powder and the glass fiber; then the mixture is placed in an oven at 80 to 90℃ for secondary drying for 20 to 25 hours;

[0011] (3) Molding: the modified mixture is poured into a mold, a flat vulcanizing machine is used to apply a temperature of 160 to 180℃ and a pressure of 5 to 10 MPa, and the PVC non-slip mat is obtained after cooling and demolding.

[0012] Preferably, the plant powder is selected from at least one of wood powder, bamboo powder, rice husk powder, and coconut shell powder.

[0013] Preferably, the inorganic filler is selected from at least one of talc powder, wollastonite or nano calcium carbonate.

[0014] Preferably, the heat stabilizer is selected from calcium zinc stabilizer or tin stabilizer.

[0015] Preferably, the antioxidant is selected from antioxidant type 1010, 1076 or 168.

[0016] Preferably, the plasticizer is selected from one of dioctyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dibutyl phthalate, dimethyl phthalate, and diethyl phthalate.

[0017] Preferably, the silane coupling agent is selected from KH-550 or KH-570.

[0018] Preferably, the compatibilizer is a modified maleic anhydride grafted polyethylene, comprising the following steps:

[0019] Raw material preparation: prepare 100 parts of polyethylene, 2-5 parts of maleic anhydride, 0.2-1 part of initiator benzoyl peroxide, 0.06-0.2 part of (E)-1-pentenyl boron pinacol ester; 0.05-0.5 part of methallyl nickel chloride dimer (CAS: 12145-60-7) by weight;

[0020] Raw material pretreatment: dry the polyethylene at 70-90°C for 3-5 hours to remove moisture, and recrystallize and purify the maleic anhydride;

[0021] Raw material mixing: add the pretreated raw materials to a high-speed mixer and stir at a speed of 800-1200 rpm for 8-15 minutes to mix the raw materials thoroughly;

[0022] Grafting reaction: add the mixed raw materials to a twin-screw extruder, set the temperature of each section of the extruder to zone 1 150-170°C, zone 2 160-180°C, zone 3 170-190°C, zone 4 180-200°C, zone 5 190-210°C, and the screw speed to 80-120 rpm, and the reaction time to 3-7 minutes;

[0023] Product processing: after extrusion, the product is cooled with water, cut into particles, and then dried at 50-70°C for 5-8 hours to obtain the modified maleic anhydride grafted polyethylene product.

[0024] Preferably, the holding time of the compression molding is 6 to 12 minutes, and the cooling time of the compression molding is 4 to 8 minutes.

[0025] Compatibilizer reaction mechanism:

[0026] Radical initiation: through the action of the initiator, maleic anhydride, (E)-1-pentenyl boron pinacol ester CAS No. 161395-96-6, and methallyl nickel chloride dimer CAS: 12145-60-7, graft modification of polyethylene is carried out under the action of the initiator, obtaining a borane and nickel-doped compatibilizer for long-lasting wear-resistant PVC anti-slip mats. During the grafting process, borane and nickel ions are introduced, which coordinate with maleic anhydride monomers or grafting products, thereby changing their electronic structure and reactivity. The polar groups in the grafting product can interact with the polar groups of another polymer (such as polyvinyl chloride), improving the compatibility between the two.

[0027] Technical effects of compatibilizer:

[0028] Improving material toughness: the borane and nickel-doped compatibilizer can significantly improve the toughness of the PVC anti-slip mat, making it more wear-resistant and tear-resistant during use.

[0029] Enhanced interfacial adhesion: By enhancing the interfacial adhesion between PVC and polyethylene, the uniformity and stability of the blend are improved, and the occurrence of phase separation is reduced.

[0030] Improved processing performance: Borane and nickel-doped compatibilizers can improve the processing performance of PVC anti-slip mats, reduce melt viscosity, and increase extrusion speed and molding efficiency.

[0031] The PVC anti-slip mat prepared by the method provided by this invention has the following significant technical effects:

[0032] 1. Significantly improves the wear resistance of the material: By introducing plant-based powder and glass fiber into the PVC matrix and modifying it with silane coupling agent, a strong interfacial bond is formed between the filler surface and the matrix, which improves the overall stability of the material during friction.

[0033] 2. Enhanced mechanical properties of the material: Glass fiber is used as a reinforcing agent to form an efficient stress transfer network in the PVC matrix. The interfacial bonding force between the filler and the matrix is ​​further enhanced through the chemical reaction of the coupling agent, thereby improving the tensile strength and impact resistance of the material.

[0034] 3. Improved dispersibility and processing performance of fillers: Anhydrous ethanol as a solvent reduces mixing resistance, and silane coupling agents improve the dispersibility and compatibility of fillers in the matrix through chemical bonding; high-speed stirring and optimized molding process further ensure uniform distribution of fillers. Detailed Implementation

[0035] The present invention will be further illustrated by the following examples. This embodiment is implemented based on the technical solution of the present invention, and provides detailed implementation methods and processes; however, the scope of protection of the present invention is not limited to the following embodiments.

[0036] Unless otherwise specified, the experimental methods in the following examples are generally performed under conventional conditions, and the raw materials and reagents used are all commercially available products unless otherwise specified.

[0037] Example 1

[0038] (1) Raw material pretreatment: Weigh 20kg wood flour, 60kg PVC, 15kg glass fiber, 3kg talc, 2kg RUP-108 calcium zinc stabilizer, 2kg 1010 antioxidant, and 2kg dioctyl phthalate (DOP). Place the raw materials in an 85℃ oven and dry for 12 hours.

[0039] (2) Mixing and modification: Add 8kg of anhydrous ethanol, 2kg of KH-550 silane coupling agent and 1kg of compatibilizer, stir at 1800 rpm for 15 minutes, and then dry at 85℃ for 22 hours.

[0040] The preparation method of the compatilizer is as follows: 100 kg of polyethylene, 2 kg of maleic anhydride, 0.3 kg of benzoyl peroxide, 0.08 kg of (E)-1-pentenylboronic pinacol ester, and 0.1 kg of methallyl nickel chloride dimer are prepared. The polyethylene is dried at 70°C for 5 hours, and the maleic anhydride is purified by recrystallization. The raw materials are mixed at 800 rpm for 12 minutes, and then added to a twin-screw extruder (zone 1: 155°C, zone 2: 165°C, zone 3: 175°C, zone 4: 185°C, zone 5: 195°C) at a screw speed of 85 rpm, and reacted for 5 minutes. After the product is cooled by water and granulated, it is dried at 55°C for 7 hours.

[0041] (3) Molding: The mold is heated to 170°C in a flat vulcanizing machine, and a pressure of 8 MPa is applied for 8 minutes. After cooling for 6 minutes, the mold is demolded to obtain the anti-skid pad.

[0042] Example 2

[0043] (1) Raw material pretreatment: 25 kg of bamboo powder, 70 kg of PVC, 12 kg of glass fiber, 2 kg of wollastonite, 1 kg of 181 organotin stabilizer, 1 kg of 1076 antioxidant, and 1 kg of butyl benzyl phthalate (BBP) are weighed. The raw materials are dried in an 80°C oven for 15 hours.

[0044] (2) Mixing and modification: 6 kg of anhydrous ethanol, 1.5 kg of KH-570 silane coupling agent, and 1.5 kg of compatilizer are added, and stirred at 1600 rpm for 12 minutes, and then dried at 90°C for 20 hours.

[0045] The preparation method of the compatilizer is as follows: 100 kg of polyethylene, 2 kg of maleic anhydride, 0.3 kg of benzoyl peroxide, 0.08 kg of (E)-1-pentenylboronic pinacol ester, and 0.1 kg of methallyl nickel chloride dimer are prepared. The polyethylene is dried at 70°C for 5 hours, and the maleic anhydride is purified by recrystallization. The raw materials are mixed at 800 rpm for 12 minutes, and then added to a twin-screw extruder (zone 1: 155°C, zone 2: 165°C, zone 3: 175°C, zone 4: 185°C, zone 5: 195°C) at a screw speed of 85 rpm, and reacted for 5 minutes. After the product is cooled by water and granulated, it is dried at 55°C for 7 hours.

[0046] (3) Molding: The mold is heated to 175°C, and a pressure of 7 MPa is applied for 10 minutes. After cooling for 5 minutes, the mold is demolded.

[0047] Example 3

[0048] (1) Raw material pretreatment: take 15 kg of coconut shell powder, 75 kg of PVC, 18 kg of glass fiber, 4 kg of nano calcium carbonate, 3 kg of CZX-682 type calcium zinc stabilizer, 3 kg of 168 antioxidant, and 3 kg of dibutyl phthalate (DBP). Dry the raw materials in a 90°C oven for 10 hours.

[0049] (2) Mixing and modification: add 10 kg of anhydrous ethanol, 3 kg of KH-550 silane coupling agent, and 2 kg of compatibilizer, stir at 2000 rpm for 10 minutes, and then dry at 80°C for 25 hours.

[0050] The preparation method of the compatibilizer is as follows: prepare 100 kg of polyethylene, 3 kg of maleic anhydride, 0.5 kg of benzoyl peroxide, 0.15 kg of (E)-1-pentenyl boron pinacol ester, and 0.2 kg of methallyl nickel chloride dimer. Dry the polyethylene at 90°C for 3.5 hours, and then mix the purified maleic anhydride with the raw materials at 1100 rpm for 9 minutes. The temperature of the double-screw extruder is 165°C in the first zone, 175°C in the second zone, 185°C in the third zone, 195°C in the fourth zone, and 205°C in the fifth zone, with a screw speed of 110 rpm. The reaction time is 6 minutes. After the product is cut into granules by water cooling, it is dried at 60°C for 6.5 hours.

[0051] (3) Molding: the mold is at 180°C, 10 MPa pressure for 6 minutes, and then demolded after cooling for 8 minutes.

[0052] Example 4

[0053] (1) Raw material pretreatment: take 30 kg of rice husk powder, 50 kg of PVC, 20 kg of glass fiber, 1 kg of talc powder, 5 kg of Mark 17MOK-N type tin stabilizer, 1 kg of 1010 antioxidant, and 1 kg of diethyl phthalate (DEP). Dry the raw materials in an 82°C oven for 14 hours.

[0054] (2) Mixing and modification: add 5 kg of anhydrous ethanol, 1 kg of KH-570 silane coupling agent, and 3 kg of compatibilizer, stir at 1500 rpm for 20 minutes, and then dry at 85°C for 24 hours.

[0055] The preparation method of the compatibilizer is as follows: prepare 100 kg of polyethylene, 5 kg of maleic anhydride, 0.9 kg of benzoyl peroxide, 0.18 kg of (E)-1-pentenyl boron pinacol ester, and 0.45 kg of methallyl nickel chloride dimer. Dry the polyethylene at 75°C for 4.5 hours, and then mix the purified maleic anhydride with the raw materials at 1200 rpm for 8 minutes. The temperature of the double-screw extruder is 170°C in the first zone, 180°C in the second zone, 190°C in the third zone, 200°C in the fourth zone, and 210°C in the fifth zone, with a screw speed of 95 rpm. The reaction time is 3 minutes. After the product is cut into granules by water cooling, it is dried at 70°C for 5 hours.

[0056] (3) Compression molding: The mold was kept at 160°C under a pressure of 5 MPa for 12 minutes, and then demolded after cooling for 4 minutes.

[0057] Comparative Example 1

[0058] In this example, no compatibilizer was added, and the rest was the same as in Example 1.

[0059] Comparative Example 2

[0060] In this example, no (E)-1-pentenylboronic acid pinacol ester was added during the preparation of the compatibilizer, and the rest was the same as in Example 1.

[0061] Comparative Example 3

[0062] In this example, no methallyl nickel chloride dimer was added during the preparation of the compatibilizer, and the rest was the same as in Example 1.

[0063] Test Method:

[0064] 1) Abrasion Resistance Test

[0065] Test Equipment: Taber Abrasion Tester.

[0066] Test Conditions: Abrasion Wheel Type: H-18; Load: 500 g; Number of Revolutions: 1000.

[0067] Test Standard: According to ASTM D4060 standard, record the mass loss (mg) after abrasion.

[0068] 2) Tensile Strength Test:

[0069] Test Equipment: Electronic Tensile Testing Machine.

[0070] Test Conditions: Sample Size: Standard Dumbbell-Shaped Sample; Tensile Speed: 50 mm / min; Environmental Conditions: 23°C, Relative Humidity 50%.

[0071] Test Standard: According to ISO 527 standard, determine the tensile strength (MPa) of the sample.

[0072] 3) Slip Resistance Test

[0073] Test Equipment: Friction Coefficient Tester.

[0074] Test Conditions: Spray a thin film of water on the surface of the material; Load Pressure: 250 N; Test Plate Inclination Angle: 15°.

[0075] Test Standard: According to GB / T 30106 standard, determine the static friction coefficient.

[0076] Test Results:

[0077] Table 1: Test Results of Examples and Comparative Examples

[0078] Wear resistance (mg) Tensile strength MPa Static friction coefficient Example 1 15.6 25.8 0.72 Example 2 15.3 26.1 0.73 Example 3 14.8 26.6 0.75 Example 4 14.4 26.9 0.75 Comparative Example 1 17.7 23.0 0.69 Comparative Example 2 15.9 25.2 0.71 Comparative Example 3 16.3 24.7 0.70

[0079] In summary, the test results of the examples and the comparative examples show that the wear resistance, mechanical properties and anti-skid performance of the PVC anti-skid pad are significantly improved, and the examples have excellent technical effects and industrial application value.

[0080] The above embodiments are the preferred implementation of the present application, in addition to this, the present application can be implemented in other ways, without departing from the concept of the present application, any obvious replacement within the protection scope of the present application.

Claims

1. A method for preparing long-lasting wear-resistant PVC non-slip mat, characterized in that, The method comprises the following steps: (1) raw material pretreatment: 15 to 30 parts by weight of plant powder, 50 to 75 parts of PVC, 10 to 20 parts of glass fiber, 1 to 5 parts of inorganic filler, 1 to 3 parts of heat stabilizer, 1 to 3 parts of antioxidant and 1 to 3 parts of plasticizer are weighed, and the raw materials are dried in an oven at 80 to 90°C for 10 to 15 hours; (2) mixing and modification: 5 to 10 parts of anhydrous ethanol and 1 to 3 parts of silane coupling agent, 1 to 3 parts of compatibilizer are added to the dried raw materials, and the mixture is stirred by a high-speed stirring device at 1500 to 2000 rpm for 10 to 20 minutes to ensure that the silane coupling agent is uniformly coated on the surface of the plant powder and the glass fiber; then the mixture is placed in an oven at 80 to 90°C for secondary drying for 20 to 25 hours; (3) compression molding: the modified mixture is poured into a mold, a flat vulcanizing machine is used to apply a temperature of 160 to 180°C and a pressure of 5 to 10 MPa, and the product is demolded after cooling to obtain the PVC non-slip mat; The compatibilizer is modified maleic anhydride grafted polyethylene, which is prepared by the reaction of polyethylene, maleic anhydride, initiator benzoyl peroxide, (E)-1-pentenyl boron pinacol ester and methallyl nickel chloride dimer.

2. The method of claim 1, wherein the long-lasting wear-resistant PVC non-slip mat is prepared by the following steps: The plant powder is at least one selected from wood powder, bamboo powder, rice husk powder and coconut shell powder.

3. The method of claim 1, wherein the long-lasting wear-resistant PVC non-slip mat is prepared by the following steps: The inorganic filler is at least one selected from talc, wollastonite or nano calcium carbonate.

4. The method of claim 1, wherein the long-lasting wear-resistant PVC non-slip mat is prepared by the following steps: The heat stabilizer is selected from calcium-zinc stabilizer or tin stabilizer.

5. The method of claim 1, wherein the long-lasting wear-resistant PVC non-slip mat is prepared by the following steps: The antioxidant is selected from antioxidant 1010, 1076 or 168.

6. The method of claim 1, wherein the long-lasting, wear-resistant PVC non-slip mat is prepared by the following steps: The plasticizer is selected from one of dioctyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dibutyl phthalate, dimethyl phthalate and diethyl phthalate.

7. The method of claim 1, wherein the long-lasting wear-resistant PVC non-slip mat is prepared by the following steps: The silane coupling agent is selected from KH-550 or KH-570.

8. The method of claim 1, wherein the long-lasting, wear-resistant PVC non-slip mat is prepared by the following steps: The compatibilizer is modified maleic anhydride grafted polyethylene, which comprises the following steps: Raw material preparation: 100 parts by weight of polyethylene, 2-5 parts of maleic anhydride, 0.2-1 part of initiator benzoyl peroxide, 0.06-0.2 part of (E)-1-pentenyl boron pinacol ester and 0.05-0.5 part of methallyl nickel chloride dimer are prepared; Raw material pretreatment: the polyethylene is dried at 70-90°C for 3-5 hours to remove moisture, and the maleic anhydride is recrystallized and purified; Raw material mixing: the pretreated raw materials are added to a high-speed mixer and stirred at a speed of 800-1200 rpm for 8-15 minutes to fully mix the raw materials; Grafting reaction: the mixed raw materials are added to a twin-screw extruder, the temperature of each section of the extruder is set to zone 1 150-170°C, zone 2 160-180°C, zone 3 170-190°C, zone 4 180-200°C and zone 5 190-210°C, the screw rotation speed is 80-120 rpm, and the reaction time is 3-7 minutes; Product treatment: the extruded product is water-cooled, granulated and dried at 50-70°C for 5-8 hours to obtain the modified maleic anhydride grafted polyethylene product.

9. The method for preparing the long-lasting wear-resistant PVC anti-slip mat according to claim 1, characterized in that: The pressure holding time of the compression molding is 6 to 12 minutes, and the cooling time of the compression molding is 4 to 8 minutes.